JP7519093B2 - Laminated film, method for producing laminated film, method for producing article with film, and resin composition - Google Patents

Description

The present invention relates to a laminated film, a method for manufacturing a laminated film, a method for manufacturing an article with a film, and a resin composition.

In recent years, a method of laminating a film such as a protective film or decorative film to the surface of an article has been used as an alternative to directly applying paint to the article for surface protection or decoration. Examples of articles for which the above-mentioned films are used include personal computers, smartphones, plastic products used as daily necessities, and interior and exterior components of automobiles. Specific examples of the above-mentioned films include laminated films supplied to the market, such as car wrapping films that are applied to the painted surfaces of automobiles and motorcycles to add design, and paint protection films that protect the painted surfaces of automobiles from flying stones and dirt.

The above-mentioned film is used by being attached to an article, and therefore is required to have shape-following properties according to the three-dimensional shape of the article, as well as a function for protecting the article. For example, Patent Document 1 discloses a film made of a thermosetting polyurethane resin that is a crosslinked product of a composition containing a hydroxyl group-containing copolymer and a polyisocyanate made of a vinyl compound having a ring-opening lactone group, etc., as a film having abrasion resistance and contamination resistance. The film of Patent Document 1 has an abrasion recovery property in which it immediately undergoes elastic deformation when external pressure is applied to the film surface, does not easily break, and recovers from the deformation without remaining as plastic deformation after the external pressure is removed.

The film of Patent Document 1 is a substrate-less film obtained by applying the above-mentioned composition to the main surface of a release film made of a thermoplastic resin film, crosslinking the composition by heating, and then peeling off the release film.

JP 2012-197377 A

In recent years, there has been a demand for high designability while protecting articles, and at least one side of the film needs to have a dense decorative layer formed by gravure printing, inkjet printing, or the like. Also, an adhesive layer is required to attach the film to the article. When providing the film of Patent Document 1 with a functional layer such as a decorative layer or adhesive layer, a conceivable method is to form a polyurethane resin layer made of a thermoset product of the above-mentioned composition on the main surface of the release film, and then form a functional layer on the surface of the polyurethane resin layer.

When a laminated film is formed by sequentially laminating a release film, a polyurethane resin layer, and a functional layer, the polyurethane resin layer is required to have low adhesion to the release film so that it can be peeled off, and high adhesion to the functional layer so that peeling does not occur. On the other hand, a polyurethane resin layer made of a thermosetting polyurethane has a property of high adhesion to a release film. In particular, many thermosetting polyurethane resin layers having scratch recovery have a low peak top temperature of the loss tangent obtained by dynamic viscoelasticity measurement and are flexible, so that the property of high adhesion to a release film is more prominent. Therefore, in the past, a release film with low adhesion, such as a film made of a material with low adhesion or a film that has been subjected to a release treatment that reduces adhesion, has been selected as the release film in accordance with the high adhesion of the thermosetting polyurethane resin layer. However, in this case, the types of release films that can be used are limited, and the degree of freedom in selecting a release film is significantly reduced.

This invention was made in consideration of these circumstances, and its purpose is to provide a laminated film having a thermosetting polyurethane resin layer that has peelable adhesion to a release film provided on one surface, while having adhesion to a functional layer provided on the other surface that does not easily peel off during formation, etc.

The laminated film that solves the above problem comprises a release film and a main film peelably adhered to the first main surface of the release film, the main film comprises a polyurethane resin layer adhered to the release film, and is a processing film that is used by forming a functional layer made of a functional component on the surface of the polyurethane resin layer, the polyurethane resin layer is a thermoset of a resin composition containing at least one of (A) a (meth)acrylic resin having a hydroxyl group and (B) a polyol, (C) a polyfunctional isocyanate, and (D) a modified polydialkylsiloxane compound, the modified polydialkylsiloxane compound (D) being a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure, and the polyurethane resin layer has a peak top temperature of loss tangent of -80°C or higher obtained by dynamic viscoelasticity measurement at a frequency of 1.0 Hz and a temperature range of -120 to 250°C.

The laminated film that solves the above problem comprises a release film and a main film peelably adhered to the first main surface of the release film, the main film comprises a polyurethane resin layer adhered to the release film, and a functional layer made of a functional component formed on the surface of the polyurethane resin layer opposite the release film, the polyurethane resin layer is a thermoset of a resin composition containing at least one of (A) a (meth)acrylic resin having a hydroxyl group and (B) a polyol, (C) a polyfunctional isocyanate, and (D) a modified polydialkylsiloxane compound, the modified polydialkylsiloxane compound (D) being a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure, and the polyurethane resin layer has a peak top temperature of loss tangent of -80°C or higher obtained by dynamic viscoelasticity measurement at a frequency of 1.0 Hz and a temperature range of -120 to 250°C.

In the laminated film, the polyurethane resin layer has a peak top temperature of 90° C. or lower.
In the above laminated film, the release film preferably has a surface free energy of the first main surface of 20 to 50 mN/m.

In the above laminated film, it is preferable that the first main surface of the release film is a surface that has been subjected to a release treatment with a release agent.
In the laminated film, the release agent is preferably a non-silicone release agent.

The method for manufacturing a laminated film that solves the above problem includes a polyurethane resin layer forming step of forming the polyurethane resin layer on the first main surface of the release film, and a functional layer forming step of forming a functional layer made of a functional component on the surface of the polyurethane resin layer, the polyurethane resin layer forming step being a step of forming the polyurethane resin layer by thermally curing a resin composition containing at least one of (A) a (meth)acrylic resin having a hydroxyl group and (B) a polyol, (C) a polyfunctional isocyanate, and (D) a modified polydialkylsiloxane compound, the modified polydialkylsiloxane compound being a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure, and the polyurethane resin layer has a peak top temperature of loss tangent of -80°C or higher, obtained by dynamic viscoelasticity measurement at a frequency of 1.0 Hz and a temperature range of -120 to 250°C.

A method for manufacturing an article with a film that solves the above problem includes a lamination step of laminating a functional layer made of a functional component on the surface of the polyurethane resin layer of the laminated film, and a peeling step of peeling the release film from the laminated film before or after attaching the laminated film with the functional layer laminated thereon to an article.

The resin composition that solves the above problem is a resin composition used as a raw material for the polyurethane resin layer of the laminated film, and contains at least one of (A) a (meth)acrylic resin having a hydroxy group and (B) a polyol, (C) a polyfunctional isocyanate, and (D) a modified polydialkylsiloxane compound, and the (A) (meth)acrylic resin having a hydroxy group has a glass transition temperature of -75 to 120°C and a hydroxyl value of 20 to 150 mgKOH/g, and the (B) polyol is a polylactone polyol, a polycarbonate The polyol is selected from the group consisting of polyols, polyester polyols, and polyether polyols, has a number average molecular weight of 100 to 3000, and has two or more hydroxyl groups in one molecule, the (C) polyfunctional isocyanate has two or more isocyanate groups in one molecule, and the (D) modified polydialkylsiloxane compound is a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain bonded to the polydialkylsiloxane structure and a polyether chain.

According to the present invention, a laminated film is obtained that has a thermosetting polyurethane resin layer that has peelable adhesion to a release film provided on one surface, while having adhesion that does not easily peel off from a functional layer provided on the other surface.

FIG. 4A to 4C are explanatory views of a method for producing a laminated film. FIG. 4 is an explanatory diagram of a method for using the laminated film.

Hereinafter, one embodiment of the present invention will be described.
In this specification, the expression "a to b" in the description of a numerical range means from a to b, unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass to 5% by mass."

In this specification, when a group (atomic group) is described without specifying whether it is substituted or unsubstituted, it includes both those that have no substituents and those that have a substituent. For example, "alkyl group" includes not only alkyl groups that have no substituents (unsubstituted alkyl groups), but also alkyl groups that have a substituent (substituted alkyl groups). In this specification, the term "(meth)acrylic" represents a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate."

As shown in FIG. 1, the laminated film F of this embodiment includes a release film 10 having a first main surface 10a, and a main film 20 releasably adhered to the first main surface 10a of the release film 10.

The laminate film F is attached to the surface of an article and is used, for example, as a protection film for protecting the surface of the article or a decorative film for decorating the surface of the article.
[Release film]
The release film 10 is a film that supports the main film 20 and is peeled off when the main film 20 is attached to the surface of an article.

The release film 10 is not particularly limited, but is preferably a film in which the surface free energy of the first main surface 10a is adjusted to 20 to 50 mN/m. In this case, the upper limit of the range of the surface free energy of the first main surface 10a is preferably 45 mN/m or less. The lower limit of the range of the surface free energy of the first main surface 10a is preferably 25 mN/m or more, and more preferably 30 mN/m or more.

When the surface free energy of the first main surface 10a is 20 mN/m or more, when the main film 20 is formed by coating on the first main surface 10a of the release film 10, the formed main film 20 is less likely to have poor appearance such as poor leveling or cissing. When the surface free energy of the first main surface 10a is 50 mN/m or less, breakage of the main film 20 or poor peeling can be suppressed when peeling the release film 10 from the main film 20.

The above surface free energy can be determined according to the Owens and Wendt method (J. Appl. Polym. Sci., 13, 1741 (1969)). Specifically, a liquid with a known surface free energy is dropped onto the first main surface 10a of the release film 10, and the static contact angle at 25°C is measured using PCA-11 (manufactured by Kyowa Interface Science Co., Ltd.), and the surface free energy is calculated using a formula based on the Owens and Wendt analysis.

The static contact angle is measured at 25°C by dropping the test liquid onto the first main surface 10a of the release film 10, with a waiting time of 5 seconds from the drop to the measurement, using the θ/2 method in accordance with the "static drop method" described in JIS-R3257.

The test liquids used are water and diiodomethane. The surface free energy values of water and diiodomethane are as follows:
Water: γ _L ^d = 21.8 mN/m, γ _L ^p = 51.0 mN/m,
Diiodomethane: γ _L ^d =50.8 mN/m, γ _L ^p =0 mN/m
The Owens and Wendt analysis is intended to form the dispersion component of the surface free energy based on the following equations (1) to (3).

Formula (1): 1+cosθ=2[(γ _S ^d・γ _L ^d )/γ _L ² ] ^1/2 +2[(γ _S ^p・γ _L ^p )/γ _L ² ] ^1/2
Formula (2): γ _S = γ _S ^d + γ _S ^p
Formula (3): γ _L = γ _L ^d + γ _L ^p
θ is the contact angle with each test liquid, γ _S ^d and γ _L ^d are the dispersion components of the surface free energy between the release film 10 and the test liquid, and γ _S ^p and γ _L ^p are the dispersion components of the surface free energy between the release film 10 and the test liquid. and the polar component of the surface free energy of the test liquid.

By inserting these values into the above formulas (1) to (3) and then inserting the values of the contact angles using each test liquid into the above formulas, the surface free energy γ _S can be calculated.
Examples of materials for the release film 10 include polyethylene terephthalate resin, polyolefin resin, polycarbonate resin, acrylic resin, polyvinyl chloride resin, cellulose resin, cycloolefin polymer resin, polyimide resin, and paper made of fibrous materials such as natural fibers and synthetic fibers.

As the release agent 11 used in the release treatment, a silicone-based release agent and a non-silicone-based release agent can be used. Examples of non-silicone-based release agents include fluorine-based release agents, acrylic-based release agents, vinyl-based release agents, alkyd-based release agents, melamine-based release agents, and acrylic-based release agents having long-chain alkyl groups. The release agent 11 can be used alone or in combination with multiple types. Note that if the surface free energy of the first main surface 10a can be adjusted to the above range simply by selecting the material of the release film 10, the release treatment may be omitted.

[Main body film]
The main film 20 includes a polyurethane resin layer 21 adhered to the first main surface 10a of the release film 10, and a functional layer 22 adhered to the surface of the polyurethane resin layer 21. In this embodiment, the functional layer 22 is adhered to the surface of the polyurethane resin layer 21 opposite to the release film 10.

(Polyurethane resin layer)
The polyurethane resin layer 21 is a thermosetting product of a resin composition containing at least one of (A) a (meth)acrylic resin having a hydroxyl group and (B) a polyol, (C) a polyfunctional isocyanate, and (D) a modified polydialkylsiloxane compound. The polyurethane resin layer 21 is a protective layer for protecting the surface of the target article, and is preferably a protective layer having excellent flexibility that can impart functions such as weather resistance and scratch recovery to the surface of the target article. Scratch recovery means a function of naturally recovering to the original shape so that even if a small scratch occurs in the polyurethane resin layer 21, the scratch is filled. The polyurethane resin layer 21 may be a polyurethane resin layer that does not have scratch recovery.

The polyurethane resin layer 21 has a peak top temperature of the loss tangent (tan δ) (hereinafter simply referred to as the peak top temperature) obtained by dynamic viscoelasticity measurement at a frequency of 1.0 Hz and a temperature range of -120 to 250°C set to a specific temperature range described below. If there are multiple loss tangent peaks within the temperature range, the peak top temperature of the peak with the highest peak top value is treated as the peak top temperature.

The peak top temperature is -80°C or higher, preferably -60°C or higher, more preferably -45°C or higher, and even more preferably -35°C or higher. The upper limit of the peak top temperature is, for example, 120°C.

When a flexible polyurethane resin layer 21 having scratch recovery properties is to be formed, the peak top temperature is 100°C or less, preferably 90°C or less, more preferably 70°C or less, even more preferably 65°C or less, and even more preferably 55°C or less.

The peak top temperature of the polyurethane resin layer 21 can be controlled, for example, by adjusting the ratio of each component contained in the resin composition and by adjusting the hydroxyl value of each component. For example, when the glass transition temperature of the (meth)acrylic resin having a hydroxy group (A) is adjusted to increase the glass transition temperature, the peak top temperature of the polyurethane resin layer 21 tends to increase, and when the glass transition temperature is decreased, the peak top temperature of the polyurethane resin layer 21 tends to decrease.

The thickness of the polyurethane resin layer 21 is, for example, 5 to 500 μm, preferably 5 to 300 μm, more preferably 10 to 240 μm, and further preferably 20 to 160 μm.
The resin composition for forming the polyurethane resin layer 21 will be described in detail below.

<Component A: (meth)acrylic resin having a hydroxy group>
The component A contained in the resin composition is a polymer containing a structural unit derived from a (meth)acryloyl group-containing monomer and having a hydroxyl group. The (meth)acryloyl group-containing monomer is (meth)acrylic acid and/or a (meth)acrylic acid ester, specifically, a monomer having a structure represented by the following formula (1).

In formula (1), R represents a hydrogen atom or a methyl group, and R' represents a hydrogen atom or an optionally substituted organic group.

The position at which the hydroxyl group is bonded in component A may be any of the side chain, main chain, terminal, etc. For reasons such as ease of synthesis, ease of adjusting the hydroxyl value, and ease of distributing hydroxyl groups uniformly in component A, it is preferable that the bonding position of the hydroxyl group is at least the side chain of component A, that is, component A has a constituent unit derived from a monomer in which a hydroxyl group is substituted for the organic group R' in the above formula (1).

It is preferable that component A contains, as its constituent units, constituent units derived from a (meth)acryloyl group-containing monomer having a structure selected from the group consisting of polylactone, polycarbonate, polyester, and polyether (hereinafter also referred to as "(a1) structure").

・Constituent unit having (a1) structure The (a1) structure selected from the group consisting of polylactone, polycarbonate, polyester and polyether contained in the A component is a flexible structure that imparts flexibility to the A component. By containing the (a1) structure in the A component, excellent scratch recovery of the polyurethane resin layer 21 can be obtained. The A component may contain one or more of polylactone, polycarbonate, polyester and polyether as the (a1) structure. Among these (a1) structures, polylactone, polycarbonate and polyester are preferred, polylactone and polycarbonate are more preferred, and polylactone is even more preferred.

An example of the polylactone structure is the structure represented by the following formula (2), an example of the polycarbonate structure is the structure represented by the following formula (3), an example of the polyester structure is the structure represented by the following formula (4), and an example of the polyether structure is the structure represented by the following formula (5).

In formulas (2) and (3), ^X1 is a linear or branched alkylene group, preferably a linear alkylene group, and the number of carbon atoms therein is preferably 3 to 7, more preferably 4 to 6, and even more preferably 5. In addition, n is an integer of 1 or more, preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 5.

In formula (4), ^X2 and ^X3 may be the same or different and are selected from linear or branched alkylene groups and organic groups containing aromatic groups, and are preferably linear alkylene groups, and the number of carbon atoms in the linear or branched alkylene group is preferably 3 to 7, more preferably 4 to 6, and even more preferably 5. In addition, n is an integer of 1 or more, and is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 5.

In formula (5), ^X4 and ^X5 are linear or branched alkylene groups (preferably linear alkylene groups) which may be the same or different, and the number of carbon atoms is preferably 2 to 7, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 2. The sum of l and m is preferably 1 to 20, more preferably 2 to 10, even more preferably 2 to 8, and even more preferably 2 to 5.

Among the structures shown in formulas (2) to (5), the polylactone shown in formula (2), the polycarbonate shown in formula (3), and the polyether shown in formula (5) are preferred in that the structures can form terminal hydroxyl groups, making the effects of the present invention even more favorable. In these cases, the (meth)acryloyl group-containing monomer used in the synthesis of component A is composed of a polylactone, polycarbonate, and polyether whose R' in formula (1) contains a terminal hydroxyl group and is shown in the following formulas (2a), (3a), and (5a), respectively.

In formula (2a), X ¹ is as described in formula (2). X ⁶ is a linear or branched alkylene group (preferably a linear alkylene group), and the number of carbon atoms is preferably 2 to 7, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 2. Furthermore, n is as described in formula (2). In formula (3a), X ¹ is as described in formula (3). Furthermore, X ⁷ is a linear or branched alkylene group (preferably a linear alkylene group), and the number of carbon atoms is preferably 2 to 7, more preferably 2 to 5, and even more preferably 2 to 4. Furthermore, n is as described in formula (3). In formula (5a), X ⁴ and X ⁵ , and l and m are as described in formula (5).

Commercially available (meth)acryloyl group-containing monomers having the flexible structure shown in formula (2a) include, for example, the PLACCEL F series (polycaprolactone-modified hydroxy(meth)acrylate) manufactured by Daicel Corporation, and preferably, PLACCEL FA2D (polycaprolactone-modified hydroxyethyl acrylate; 2-mol adduct of caprolactone), PLACCEL FA5 (polycaprolactone-modified hydroxyethyl acrylate; 5-mol adduct of caprolactone), PLACCEL FM2D (polycaprolactone-modified hydroxyethyl methacrylate; 2-mol adduct of caprolactone), and PLACCEL FM5 (polycaprolactone-modified hydroxyethyl methacrylate; 5-mol adduct of caprolactone). Examples of the (meth)acryloyl group-containing monomer having a flexible structure and a hydroxyl group represented by formula (3a) include a commercially available mixture of (meth)acrylic acid (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-alkyl ester and methacrylic acid 2-hydroxyethyl ester, such as Plaxel HEMAC1 manufactured by Daicel Corporation. Commercially available (meth)acryloyl group-containing monomers having a flexible structure and a hydroxyl group as shown in formula (5a) include, for example, NOF Corporation's Blemmer PE-90, 200, 350, 350G, 1000, 500, and 800 (polyethylene glycol monomethacrylate), Blemmer 50E-300 (polyethylene glycol-propylene glycol-monomethacrylate), Blemmer 55PET-800 (polyethylene glycol-tetramethylene glycol-monomethacrylate), Blemmer 10PPB-500B (propylene glycol-polybutylene glycol-monomethacrylate), Blemmer AE-90U, 200, and 400 (polyethylene glycol monoacrylate), and Blemmer AP-400, 550, and 800 (polypropylene glycol monoacrylate).

In the synthesis of the component A, these monomers having the (a1) structure may be used alone or in combination of two or more.
The chain length of the (a1) structure is not particularly limited, and may be, for example, a structure having a long chain length (n in the above formulas (2) to (5) is, for example, 4 or more, preferably 5 or more) or a structure having a short chain length (n in the above formulas (2) to (5) is, for example, 3 or less, preferably 2 or less). Furthermore, the component A may contain a combination of structures having different chain lengths as the (a1) structure. The (a1) structure imparts excellent scratch recovery to the polyurethane resin layer 21 due to its flexibility, and therefore tends to exhibit better scratch recovery as the chain length becomes longer (n in the above formulas (2) to (5) is, for example, 4 or more, preferably 5 or more).

The amount (total amount) of structural units having the (a1) structure per 100 parts by mass of component A is not particularly limited, but may be, for example, 10 to 60 parts by mass. Furthermore, from the viewpoint of obtaining even more preferable scratch recovery, the lower limit of the range of the amount of the structural units is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more. The upper limit of the range of the amount of the structural units is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.

Other Structural Units The component A may contain at least any one of a structural unit derived from a (meth)acryloyl group-containing monomer having a hydroxyl group, a structural unit derived from a (meth)acryloyl group-containing monomer not having a hydroxyl group, and a structural unit derived from a monomer other than the (meth)acryloyl group-containing monomer, other than the structural unit having the (a1) structure.

An example of a structural unit derived from a (meth)acryloyl group-containing monomer having a hydroxyl group is a structural unit derived from a monomer in which R' in the above formula (1) is a hydroxyalkyl group having 1 to 6 carbon atoms. Examples of hydroxyalkyl groups having 1 to 6 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group, and more preferably, a hydroxy chain alkyl group such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group, and even more preferably, a 2-hydroxyethyl group and a 4-hydroxy-n-butyl group.

Component A can contain one or more of these monomer-derived constitutional units.
When component A contains a structural unit derived from a (meth)acryloyl group-containing monomer having a hydroxyl group other than the structural unit having the (a1) structure, the amount of the structural unit per 100 parts by mass of component A can be appropriately set depending on the hydroxyl value that component A must satisfy, and is, for example, 3 to 35 parts by mass, preferably 5 to 25 parts by mass, and more preferably 5 to 15 parts by mass.

Specific examples of (meth)acryloyl group-containing monomers that do not contain hydroxyl groups include (meth)acrylic acid and (meth)acrylic acid esters. When component A has structural units derived from (meth)acryloyl group-containing monomers that do not contain hydroxyl groups, component A can contain structural units derived from either or both of (meth)acrylic acid and (meth)acrylic acid esters, and preferably contains structural units derived from both.

Component A can contain structural units derived from either or both of structural units derived from acrylic acid and structural units derived from methacrylic acid.
When the A component contains a structural unit derived from (meth)acrylic acid, the amount of the structural unit derived from (meth)acrylic acid per 100 parts by mass of the A component is, for example, 0.3 to 3.0 parts by mass, preferably 0.3 to 1.5 parts by mass, and more preferably 0.6 to 1.2 parts by mass.

(Meth)acrylic acid esters are monomers in which R' in formula (1) is a monovalent alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group. Examples of monovalent alkyl groups include linear or branched alkyl groups having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 4 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, and decyl groups.

The number of carbon atoms in monocyclic and polycyclic (e.g., bridged or condensed rings such as two, three, four, five, and six) cycloalkyl groups is, for example, 3 to 20, preferably 4 to 15, more preferably 5 to 12, and even more preferably 6 to 9. Specific examples of monocyclic structures include cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane. Specific examples of polycyclic structures include bicyclic alkanes such as norbornane, isobornane, bicycloundecane, and decahydronaphthalene (decalin); and polycyclic hydrocarbons with two or more rings such as dicyclopentanyl, cubane, basketane, hausane, and adamantane.

Specific examples of (meth)acryloyl group-containing monomers having a monocyclic or polycyclic cycloalkyl group include esters of (meth)acrylic acid and alcohols having a monocyclic or polycyclic cycloalkyl group, i.e., those in which R' in the above formula (1) is a monovalent group of the above alicyclic structure. More specific examples include (meth)acrylic acid cycloalkyl esters such as cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, cyclononyl (meth)acrylate, cyclodecyl (meth)acrylate, cycloundecyl (meth)acrylate, and cyclododecyl (meth)acrylate; norbornyl (meth)acrylate, isobornyl (meth)acrylate, bicycloundecyl (meth)acrylate, decahydronaphthyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and adamantyl (meth)acrylate.

Commercially available (meth)acryloyl group-containing monomers having a monocyclic or polycyclic cycloalkyl group include Blenmar CHMA manufactured by NOF Corporation, FA-513AS and FA-513M manufactured by Showa Denko Materials, Light Ester IB-X and Light Acrylate IB-XA manufactured by Kyoeisha Chemical, and MADA and MADMA manufactured by Osaka Organic Chemical Industry Co., Ltd.

Component A can contain one or more, preferably more than one, of these monomer-derived structural units.
When the A component contains a structural unit derived from a (meth)acrylic acid ester, the total amount of the structural units derived from a (meth)acrylic acid ester per 100 parts by mass of the A component is, for example, 2 to 95 parts by mass, preferably 2 to 85 parts by mass, more preferably 2 to 75 parts by mass, and even more preferably 2 to 60 parts by mass.

When component A contains structural units derived from (meth)acrylic acid and (meth)acrylic acid ester, the total amount of (meth)acrylic acid monomer and (meth)acrylic acid ester monomer used per 100 parts by mass of component A is, for example, 2 to 98 parts by mass, preferably 2 to 88 parts by mass, and more preferably 2 to 78 parts by mass.

Monomers other than (meth)acryloyl group-containing monomers are specifically ethylenically unsaturated monomers, more specifically vinyl monomers such as vinyl acetate and vinyl propionate; unsaturated carboxylic acid monomers such as itaconic acid, maleic acid and fumaric acid; aromatic monomers such as styrene; and the like. Among these, from the viewpoint of avoiding discoloration of the cured film, the above vinyl monomers and unsaturated carboxylic acid monomers are preferred.

Component A can contain one or more of these monomer-derived constitutional units.
From the viewpoint of fully obtaining the effects derived from the component A, it is preferable that the component A does not contain structural units derived from monomers other than the (meth)acryloyl group-containing monomer. If the component A contains structural units derived from monomers other than the (meth)acryloyl group-containing monomer, the amount of structural units derived from monomers other than the (meth)acryloyl group-containing monomer per 100 parts by mass of the component A is, for example, less than 20 parts by mass, preferably less than 10 parts by mass, and more preferably less than 1 part by mass.

The synthesis of component A can also be achieved by first synthesizing a (meth)acrylic resin that does not have the (a1) structure using a (meth)acrylic monomer that does not have the (a1) structure instead of a monomer that gives a structural unit having the (a1) structure by a known polymerization method, and then modifying the (meth)acrylic resin that does not have the (a1) structure with a compound that has the (a1) structure.

The polymerization method is usually radical polymerization. The polymerization method may be any of the known polymerization methods such as solution polymerization, suspension polymerization, and emulsion polymerization. Among these polymerization methods, it is preferable to use solution polymerization from the viewpoint of precise control of polymerization.

As the polymerization initiator for radical polymerization, known initiators can be used. For example, 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(cyclohexane-1-carbonitrile) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'-azobis(4-cyanovalerate), 2,2'-azobis(2-methylbutyramide), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylamidinopropane) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methylamidinopropane] azo initiators such as 2,2'-azobis(2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); peroxide initiators such as benzoyl peroxide, t-butyl peroxy octanoate, diisobutyl peroxide, di(2-ethylhexyl) peroxy pivalate, decanoyl peroxide, t-butyl peroxy-2-ethylhexanoate, and t-butyl peroxy benzoate; and redox initiators combining an oxidizing agent and a reducing agent, such as hydrogen peroxide and an iron (II) salt, or a persulfate and sodium hydrogen sulfite. These polymerization initiators can be used alone or in combination of two or more.

Among these polymerization initiators, azo-based initiators are preferred, and 2,2'-azobis(2-methylbutyronitrile) (AMBN) and 1,1'-azobis(cyclohexane-1-carbonitrile) (ACHN) are more preferred.

The amount of the polymerization initiator used is not particularly limited, but may be, for example, 0.001 to 10 parts by mass, preferably 0.01 to 8 parts by mass, more preferably 0.1 to 6 parts by mass, and even more preferably 0.5 to 5 parts by mass per 100 parts by mass of the total amount of the monomers to be polymerized.

In addition, during the polymerization reaction, known chain transfer agents, polymerization inhibitors, molecular weight regulators, etc. may be used as appropriate. Furthermore, the polymerization reaction may be carried out in one stage or in two or more stages. The temperature of the polymerization reaction is not particularly limited, but may be, for example, 50°C to 250°C, preferably 60°C to 150°C, and more preferably 70°C to 130°C.

Molecular weight of component A The molecular weight of component A can be appropriately set according to the hydroxyl value of component A, scratch recovery, and the like. Specifically, the number average molecular weight (Mn) of component A is, for example, 1000 to 15000, preferably 3000 to 10000, and more preferably 4000 to 6000. The weight average molecular weight (Mw) of component A is, for example, 10000 to 60000, preferably 15000 to 40000, and more preferably 20000 to 35000. The polydispersity (weight average molecular weight Mw/number average molecular weight Mn) of component A is, for example, 1 to 8, preferably 1.5 to 7.5, more preferably 2 to 7, and even more preferably 3.5 to 6.5.

The number average molecular weight (Mn) and weight average molecular weight (Mw) of component A can be adjusted by adjusting conditions such as polymerization reaction time, reaction temperature, and amount of polymerization initiator used. The number average molecular weight (Mn) and weight average molecular weight (Mw) are values measured using gel permeation chromatography (GPC) in terms of standard polystyrene.

Glass Transition Temperature of Component A The glass transition temperature of component A is not particularly limited, and is, for example, −75 to 120° C. When forming a flexible polyurethane resin layer 21 having scratch recovery, the glass transition temperature of component A is, for example, −75 to 100° C., preferably −60 to 70° C., and more preferably −50 to 55° C.

The glass transition temperature of component A can be determined based on the following formula, known as the Fox formula.
1/Tg=(W ₁ /Tg ₁ )+(W ₂ /Tg ₂ )+(W ₃ /Tg ₃ )+...+(W _n /Tg _n )
In the above formula, Tg represents the glass transition temperature (K) of component A, _W1 , _W2 , _W3 ... _Wn represent the mass fractions of the monomers used in component A, and _Tg1 , _Tg2 , _Tg3 ... _Tgn represent the glass transition temperatures (K) of homopolymers obtained from monomers corresponding to the mass fractions of the monomers. Note that, according to the above formula, the glass transition temperature can be calculated using only information on monomers whose glass transition temperatures are known.

<Component B: Polyol>
The polyol as component B contained in the resin composition is a compound having two or more hydroxy groups in one molecule, except for the compound corresponding to component A. Examples of the polyol include compounds having preferably 2 to 6, and more preferably 2 to 4, hydroxy groups.

Preferred examples of component B include polylactone polyols, polycarbonate polyols, polyester polyols, and polyether polyols. These components are more appropriately flexible and have more preferable elasticity. As component B, one of polylactone polyols, polycarbonate polyols, polyester polyols, and polyether polyols may be used alone, or two or more of them may be used in combination.

The polylactone polyol is not particularly limited as long as it is a compound having a lactone ring-opening structure and two or more hydroxyl groups in one molecule, but examples include polyols represented by any of the following formulas (6a) to (6c).

In formula (6a), R ¹ represents a divalent organic group. Examples of the divalent organic group include linear alkylene groups such as -CH ₂ - and -C ₂ H ₄ -, branched alkylene groups such as -CH ₂ -C(CH ₃ ) ₂ -CH ₂ -, and ether-containing groups such as -C ₂ H ₄ -O-C ₂ H ₄ -. Each X represents a linear or branched alkylene group, which may be the same or different, and preferably a linear alkylene group. The number of carbon atoms in the alkylene group is preferably 3 to 7, more preferably 4 to 6, and even more preferably 5. Furthermore, m and n each represent an integer of 1 or more, preferably an integer of 2 to 20, and the sum of m and n is preferably 4 to 35.

In formula (6b), ^R2 represents a trivalent organic group. Examples of the trivalent organic group include a structure in which three hydrogen atoms are removed from a linear or branched alkane. Each X represents a linear or branched alkylene group, which may be the same or different, and preferably a linear alkylene group. The number of carbon atoms in the alkylene group is preferably 3 to 7, more preferably 4 to 6, and even more preferably 5. Furthermore, l, m, and n each represent an integer of 1 or more, preferably an integer of 2 to 20, and the sum of l, m, and n is preferably 3 to 40.

In formula (6c), R ³ represents a tetravalent organic group. Examples of the tetravalent organic group include a structure in which four hydrogen atoms are removed from a linear or branched alkane. Each X is a linear or branched alkylene group, which may be the same or different, and is preferably a linear alkylene group. The number of carbon atoms in the alkylene group is preferably 3 to 7, more preferably 4 to 6, and even more preferably 5. Furthermore, k, l, m, and n each represent an integer of 1 or more, preferably an integer of 2 to 20, and the sum of k, l, m, and n is preferably 4 to 50.

These polylactone polyols may be used alone or in combination of two or more.
Commercially available polylactone polyols represented by the formulae (6a) to (6c) include, for example, the PLACCEL 200 series (polycaprolactone diols), the PLACCEL 300 series (polycaprolactone triols), and the PLACCEL 400 series (polycaprolactone tetraols), manufactured by Daicel Corporation.

The polycarbonate polyol is not particularly limited as long as it is a compound having a carbonate group represented by -O-(C=O)-O- and two or more (preferably two) hydroxyl groups in one molecule. The polycarbonate polyol can be obtained by reacting one or more polyol raw materials (polyhydric alcohols) with a carbonate ester or phosgene (preferably a carbonate ester). Examples of the polyol raw materials include aliphatic polyols, alicyclic polyols, aromatic polyols, etc., preferably aliphatic polyols, more preferably linear or branched diols having 2 to 10 carbon atoms such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol. Examples of the carbonate ester include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate, aromatic carbonate esters such as diphenyl carbonate, and cyclic carbonate esters such as ethylene carbonate, preferably aliphatic carbonate esters, more preferably dimethyl carbonate.

Commercially available polycarbonate polyols include the Duranol series (polycarbonate diol) manufactured by Asahi Kasei Corporation, the ETERNACOLL UM series (polycarbonate made from 1,4-cyclohexanedimethanol and 1,6-hexanediol) manufactured by Ube Industries, Ltd., and the Kuraray Polyol C series (polycarbonate made from 3-methyl-1,5-pentanediol and 1,6-hexanediol) manufactured by Kuraray Co., Ltd.

The polyester polyol is not particularly limited as long as it is a compound having an ester group (-COO- or -OCO-) and two or more (preferably two) hydroxy groups in one molecule. The polyester polyol can be obtained by reacting one or more polyol raw materials (polyhydric alcohols) with ester-forming compounds such as polycarboxylic acids or their esters, anhydrides, and halides. Examples of the polyol raw materials include the same polyol raw materials as those used for the polycarbonate polyols described above. Examples of the ester-forming compounds such as polycarboxylic acids or their esters, anhydrides, and halides include polycarboxylic acids such as aliphatic dicarboxylic acids, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and tricarboxylic acids, acid anhydrides of these polycarboxylic acids, halides, and lower ester compounds, and more preferably, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.

These polyester polyols may be used alone or in combination of two or more.
Commercially available polyester polyols include Kuraray Polyol P Series (polyester polyols made from 3-methyl-1,5-pentanediol and one or more dicarboxylic acids selected from the group consisting of adipic acid, terephthalic acid, isophthalic acid, and sebacic acid) and Kuraray Polyol F Series (trifunctional polyester polyols made from 3-methyl-1,5-pentanediol, 1,9-nonanediol, and adipic acid) manufactured by Kuraray Co., Ltd.

The polyether polyol is not particularly limited as long as it is a compound having an ether bond (-O-) and two or more (preferably two) hydroxy groups in one molecule. Examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random copolymers or block copolymers having ethylene oxide units and propylene oxide units, and random copolymers or block copolymers having ethylene oxide units and butylene oxide units.

These polyether polyols may be used alone or in combination of two or more.
Commercially available polyether polyols include the PTMG series (polytetramethylene ether glycol) manufactured by Mitsubishi Chemical.

Molecular Weight of Component B The number average molecular weight of the polyol can be appropriately set based on the hydroxyl value of the above-mentioned component B. Specifically, the number average molecular weight of the polyol is, for example, 100 to 3000, preferably 300 to 2000, and more preferably 500 to 1500. The number average molecular weight is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

<Hydroxyl value and content of component A and component B>
Hydroxyl Values of Component A and Component B The hydroxyl value of component A is, for example, 20 to 150 mgKOH/g. When the hydroxyl value is 20 mgKOH/g or more, the crosslink density in the polyurethane resin layer 21 is prevented from becoming insufficient, making it easier to obtain sufficient coating strength. When the hydroxyl value is 150 mgKOH/g or less, the crosslink density in the polyurethane resin layer 21 is prevented from becoming excessive, making it easier to obtain flexibility.

The hydroxyl value of component B is, for example, 50 to 600 mgKOH/g. The hydroxyl value of component B is preferably 80 to 450 mgKOH/g, and more preferably 120 to 320 mgKOH/g.

When both components A and B are contained, the total hydroxyl value of components A and B (i.e., the hydroxyl value of a homogeneous mixture of components A and B) is, for example, 50 to 350 mg KOH/g.

In this specification, "hydroxyl value" refers to a value determined in accordance with the method specified in "7.1 Neutralization titration method" of JIS K 0070 "Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products." Note that the acid value is also required to calculate the hydroxyl value, and the acid value is also determined in accordance with the method specified in "3.1 Neutralization titration method" of the same JIS standard.

Contents of Component A and Component B When both Component A and Component B are contained, the contents of Component A and Component B may be appropriately determined based on the number average molecular weight and hydroxyl value described above. For example, the content of Component B per 100 parts by mass of Component A is 10 to 350 parts by mass, preferably 20 to 300 parts by mass, and more preferably 50 to 200 parts by mass.

<Component C: Polyfunctional Isocyanate>
Component C reacts with either or both of the hydroxyl groups of component A and component B to form urethane bonds, thereby hardening the polyurethane resin layer 21 .

Component C includes polyfunctional isocyanate compounds and (meth)acrylic resins copolymerized with monomers having isocyanate groups, either or both of which may be used in combination.

A polyfunctional isocyanate compound is a compound that contains two or more, preferably two to six, and more preferably two to four isocyanate groups (including isocyanate groups protected with a leaving group; the same applies below) in one molecule.

Specific examples of polyfunctional isocyanate compounds include aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; cyclic aliphatic diisocyanates such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-(or 2,6)-diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), and 1,3-(isocyanatomethyl)cyclohexane; aromatic diisocyanates such as xylylene diisocyanate and tolylene diisocyanate; and trifunctional or higher isocyanates such as lysine triisocyanate. These polyfunctional isocyanate compounds may be used alone or in combination of two or more.

It is more preferable that component C is a polymer (polyisocyanate) of the above-mentioned isocyanate compound. Examples of polyisocyanates include isocyanurate modified products [e.g., IPDI (isophorone diisocyanate) isocyanurate, HDI (hexamethylene diisocyanate) isocyanurate, etc.]; adduct modified products [e.g., trimethylolpropane adduct of TDI (tolylene diisocyanate), trimethylolpropane adduct of HDI (hexamethylene diisocyanate), trimethylolpropane adduct of xylylene diisocyanate (XDI), etc.]. adducts, trimethylolpropane adducts of IPDI (isophorone diisocyanate), etc.; biuret modified products [e.g., HDI (hexamethylene diisocyanate) biuret, etc.]; allophanate modified products [e.g., HDI (hexamethylene diisocyanate) allophanate, etc.]; prepolymers having isocyanate residues [e.g., low polymers obtained from HDI (hexamethylene diisocyanate) and polyols, etc.]. These polyisocyanates may be used alone or in combination of two or more.

Commercially available products of the above polyisocyanate compounds include, as isocyanurates of hexamethylene diisocyanate, Duranate TPA-100 and TKA-100 manufactured by Asahi Kasei Corporation, Desmodur N3300 manufactured by Bayer, Basonate HI-100 manufactured by BASF, and Coronate HX manufactured by Tosoh Corporation; as isocyanurates of isophorone diisocyanate, Vestanat manufactured by Evonik. Examples of isocyanurates of xylylene diisocyanate include Takenate D-131N manufactured by Mitsui Chemicals, Inc. Examples of adducts of hexamethylene diisocyanate include Duranate P301-75E manufactured by Asahi Kasei Corporation Examples of adducts of isophorone diisocyanate include Takenate D-140N manufactured by Mitsui Chemicals, Inc. Examples of biurets of hexamethylene diisocyanate include Takenate D-140N manufactured by Asahi Kasei Corporation. Examples of such allophanates include Duranate 24A-100, 22A-75PX, Desmodur N75 and N3200 manufactured by Bayer, Basonate HB-100 manufactured by BASF, and Toronate HDB manufactured by Vencorex; examples of allophanates of hexamethylene diisocyanate include Duranate A201H manufactured by Asahi Kasei Corporation and Takenate D-178NL manufactured by Mitsui Chemicals, Inc.; examples of prepolymers of hexamethylene isocyanate include Duranate D101 and D201 manufactured by Asahi Kasei Corporation.

Among these isocyanate compounds, preferred are isocyanurate modified compounds, adduct modified compounds, allophanate modified compounds, and prepolymer compounds, more preferred are isocyanurate of hexamethylene diisocyanate, isocyanurate of xylylene diisocyanate, adduct of hexamethylene diisocyanate, allophanate of hexamethylene diisocyanate, and prepolymer compounds of hexamethylene diisocyanate, and even more preferred is isocyanurate of hexamethylene diisocyanate.

A (meth)acrylic resin copolymerized with a monomer having an isocyanate group is a (meth)acrylic resin having two or more structural units derived from a monomer having an isocyanate group (including an isocyanate group protected by a leaving group; the same applies below) in one molecule. A (meth)acrylic resin copolymerized with a monomer having an isocyanate group can be obtained by copolymerizing a (meth)acrylic monomer and a monomer having an isocyanate group by a known method.

Examples of monomers having an isocyanate group include 2-isocyanatoethyl (meth)acrylate, [(meth)acryloyloxyalkyloxy]ethyl isocyanate, etc., and preferably 2-isocyanatoethyl (meth)acrylate.

Commercially available products of the above monomers having an isocyanate group include KarenzMOI and KarenzAOI manufactured by Showa Denko K.K. as 2-isocyanatoethyl (meth)acrylate; and KarenzMOI-EG manufactured by Showa Denko K.K. as [(meth)acryloyloxyalkyloxy]ethyl isocyanate.

Component C may be a blocked isocyanate. In particular, when the coating composition of the present invention is in the form of a one-liquid type, it is preferable that component C contains a blocked isocyanate from the viewpoint of storage stability (stability over time).

Blocked isocyanates are compounds in which some or all of the isocyanate groups of the above-mentioned isocyanate compounds are protected with leaving groups. Examples of blocking agents for forming leaving groups (protecting groups) include known blocking agents, such as phenol-based, alcohol-based, active methylene-based, mercaptan-based, acid amide-based, lactam-based, acid imide-based, imidazole-based, pyrazole-based, urea-based, oxime-based, and amine-based compounds. More specifically, examples of blocking agents include phenolic compounds such as phenol, cresol, and ethylphenol; alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol; active methylene compounds such as dimethyl malonate and acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; acid amide compounds such as acetanilide and acetate amide; lactam compounds such as ε-caprolactam and δ-valerolactam; acid imide compounds such as succinimide and maleimide; pyrazole compounds such as 3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, and 4-benzyl-3,5-dimethylpyrazole; oxime compounds such as acetaldoxime, acetoneoxime, and methylethylketoxime; and amine compounds such as diphenylaniline, aniline, and ethyleneimine.

The amount of isocyanate groups in component C can be expressed as the mass ratio of isocyanate groups (-NCO) to the entire component C. The mass ratio of isocyanate groups to component C (NCO%) is preferably 5 to 50%, more preferably 8 to 30%, even more preferably 12 to 25%, and even more preferably 16 to 23%.

The equivalent ratio (hereinafter also referred to as "isocyanate index") of the number of isocyanate groups (including blocked isocyanate groups) in component C to the total number of hydroxyl groups in components A and B is, for example, 0.5 to 1.6, preferably 0.6 to 1.4, more preferably 0.8 to 1.3, even more preferably 1.0 to 1.3, and particularly preferably 1.05 to 1.25.

<Component D: Modified polydialkylsiloxane compound>
The component D is a modified polydialkylsiloxane compound having a polydialkylsiloxane structure and a modified structure bonded to the polydialkylsiloxane structure. The component D is a component for adjusting the adhesion of the polyurethane resin layer 21 to the release film 10 and the functional layer 22.

Component D includes modified polydialkylsiloxane compounds having a polydialkylsiloxane structure bonded to a modified structure in the main chain, and modified polydialkylsiloxane compounds having a polydialkylsiloxane structure bonded to a modified structure in the side chain, either or both of which can be used in combination.

Each alkyl group in the polydialkylsiloxane structure is, for example, independently an alkyl group having 1 to 5 carbon atoms. Specific examples of polydialkylsiloxane structures include polydimethylsiloxane, polydiethylsiloxane, and polymethylethylsiloxane.

The modified structure bonded to the polydialkylsiloxane structure is at least one selected from the group consisting of polyester chains and polyether chains. It is preferable that the modified polydialkylsiloxane compound contains at least a polyether chain as a modified structure.

The polyester chain is not particularly limited as long as it has an ester bond in the main chain. The structure having an ester bond in the main chain is, for example, a structure formed by dehydration condensation of a polycarboxylic acid and a polyhydric alcohol. Examples of the polycarboxylic acid include isophthalic acid, terephthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, and adipic acid. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, glycerin, neopentyl glycol, trimethylolethane, and trimethylolpropane. Examples of the structure having an ester bond in the main chain include the structure shown in the following formula (7).

In formula (7), R ₁ , R ₂ and R ₃ each independently represent an organic group, for example, an organic group derived from the above polyvalent carboxylic acid or the above polyhydric alcohol. m represents an integer of 1 to 1000. n represents an integer of 1 to 1000.

Examples of polyether chains include poly(alkylene oxide) chains having alkylene groups with 2 to 5 carbon atoms, such as poly(ethylene oxide) chains, poly(propylene oxide) chains, and poly(ethylene oxide/propylene oxide) chains.

The bond position of the modified structure in a modified polydialkylsiloxane compound having a polydialkylsiloxane structure in the main chain is not particularly limited, and may be at the end of the chain structure formed by the polydialkylsiloxane structure, or may be within the chain. In addition, the number of bonds of the modified structure in the polydialkylsiloxane structure is not particularly limited, and may be one or more.

An example of a modified polydialkylsiloxane compound in which the modified structure is a polyether chain is polyether-modified polydialkylsiloxane. Polyether-modified polydialkylsiloxane can be obtained, for example, by addition reaction of methylhydrogenpolysiloxane and polyoxyethylene monoallyl ether in the presence of a platinum catalyst.

An example of the methylhydrogenpolysiloxane is a random copolymer having an average compositional formula represented by the following formula (8). In the following formula (8), m is an integer from 0 to 1000, n is an integer from 0 to 1000, preferably an integer from 0 to 50, and m+n is an integer from 5 to 1000, preferably an integer from 10 to 100.

The polyoxyethylene monoallyl ether may, for example, be a compound having an average compositional formula represented by the following formula (9): In the following formula (9), n represents an integer of 3 to 100, preferably an integer of 3 to 50.

_CH2 =C( _CH3 ) _{CH2CH2 -} O-( _{CH2CH2O )} n- _CH3 (9)
The content of the D component is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total of the A component and the B component. Examples include:

Commercially available modified polydialkylsiloxane compounds having a polydialkylsiloxane structure in the main chain include, for example, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-325N, BYK-326, BYK-327, BYK-330, BYK-331, BYK-333, BYK-342, BYK-370, BYK-375, BYK-377, BYK-378, BYK-3455, and BYK-3456 manufactured by BYK-Chemie. 456, BYK-3760, Shin-Etsu Chemical Co., Ltd.'s KF-1005, X-22-4952, X-22-4272, KF-6123, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-644, KF-6020, KF-6204, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X-22-2516, KF-6004, etc.

An example of a modified polydialkylsiloxane compound having a polydialkylsiloxane structure bonded to a modified structure on its side chain is a (meth)acrylic resin copolymerized with a monomer having a polydialkylsiloxane structure bonded to a modified structure.

A (meth)acrylic resin copolymerized with a monomer having a polydialkylsiloxane structure bonded to a modified structure is a (meth)acrylic resin having one or more structural units derived from a monomer having a polydialkylsiloxane structure bonded to a modified structure in one molecule. The (meth)acrylic resin can be obtained by copolymerizing a (meth)acrylic monomer with a monomer having a polydialkylsiloxane structure bonded to a modified structure by a known method.

Commercially available monomers having a polydialkylsiloxane structure bonded to a modified structure include, for example, Silaplane FM-0711 (molecular weight 1000), Silaplane FM-0721 (molecular weight 5000), Silaplane FM-0725 (molecular weight 10000), and Silaplane TM-0701T (molecular weight 423), which are methacrylic group-containing monomers manufactured by JNC Corporation.

The bonding position of the modified structure in the (meth)acrylic resin copolymerized with a monomer having a polydialkylsiloxane structure bonded to the modified structure is not particularly limited, and the number of bonds of the modified structure in the polydialkylsiloxane structure is not particularly limited, and may be one or more.

Commercially available (meth)acrylic resins in which monomers having a polydialkylsiloxane structure bonded to a modified structure are copolymerized include, for example, BYK-3550, BYK-3565, and BYK-3566 manufactured by BYK-Chemie.

In order to prevent the D component from being fixed to the surface of the polyurethane resin layer 21 and reducing the adhesion to the functional layer 22, it is preferable that the D component is not reactive to components other than the D component contained in the resin composition.

The content of component D is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass per 100 parts by mass of components A and B combined.

<Other ingredients>
The resin composition may further contain other components as necessary. Examples of the other components include active energy ray curable resins, photoinitiators, curing accelerators (curing catalysts, etc.), surfactants, ultraviolet absorbers, light stabilizers, dispersants, film-forming assistants, defoamers, viscosity regulators, and components for enhancing design (e.g., pigments, matting agents, etc.). These other components may be used alone or in combination.

<Solvent>
The resin composition may have the above-mentioned components dissolved or dispersed in a solvent. Examples of the solvent include organic solvents. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol (2-methyl-2-propanol), tert-amyl alcohol, and diacetone alcohol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate. Among these, aromatic hydrocarbon solvents, ketone solvents, and ester solvents are preferred in that they are less likely to react with polyfunctional isocyanate compounds.

The amount of the solvent is not particularly limited, but may be such that the solids (non-volatile components) concentration of the resin composition is, for example, 5 to 99% by mass, preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass.

<Form of Resin Composition>
The resin composition is obtained as a cured product of the polyurethane resin layer 21 by subjecting at least one of the components A and B to a urethane reaction with the component C in the presence of the component D. For this reason, the resin composition is appropriately prepared in a form in which the urethane reaction is controlled. The specific form of the resin composition may be either a one-component type or a two-component type.

<Method of curing resin composition (polyurethane resin layer forming step)>
As shown in Figures 2(a) and 2(b), the above resin composition is applied to the first main surface 10a of the release film 10, and then dried and cured by an appropriate method to form a polyurethane resin layer 21.

The method for applying the resin composition is not particularly limited, and it can be applied using a known coating device such as a bar coater, spray coater, air knife coater, kiss roll coater, metalling bar coater, gravure roll coater, reverse roll coater, dip coater, or die coater.

The method for drying the resin composition is not particularly limited, and any known drying technique for film coating can be appropriately applied.
The curing conditions can be appropriately set in consideration of the heat resistance of the release film 10. Examples of temperature conditions include 30 to 240°C, preferably 40 to 180°C, more preferably 50 to 160°C, and even more preferably 60 to 140°C. Examples of time conditions include 30 seconds to 80 hours, preferably 1 minute to 24 hours. In addition, in the curing, it is also possible to combine short-time baking at a higher temperature range of the above temperature conditions with long-time baking at a lower temperature range of the above temperature conditions. The curing method is not particularly limited as long as it can realize the above curing conditions, and examples include a method of exposing to hot air and a method using a drying oven (dryer) of a known coating machine.

(Functional layer)
The functional layer 22 is a layer formed on the surface of the polyurethane resin layer 21 , and is a layer for imparting an additional function to the main film 20 in addition to the protective function provided by the polyurethane resin layer 21 .

Examples of functional layer 22 include a decorative layer that imparts design, an adhesive layer that imparts adhesiveness, an anti-reflective layer that reduces reflection, an anti-bacterial/anti-viral layer that imparts anti-bacterial/anti-viral properties, and an anti-static layer that imparts anti-static properties. The decorative layer, adhesive layer, anti-reflective layer, and anti-static layer serving as functional layer 22 are not particularly limited, and any known layer contained in a film that is attached to the surface of an article can be used.

The functional layer 22 contains functional components according to the type of functional layer 22, such as pigments and inks in the case of a decorative layer, adhesives in the case of an adhesive layer, and antistatic agents in the case of an antistatic layer. The various functional components such as pigments, inks, adhesives, and antistatic agents are not particularly limited, and known components contained in films that are attached to the surface of an article can be used.

The thickness of the functional layer 22 is, for example, 0.1 to 200 μm. The thickness of the functional layer 22 is preferably set appropriately depending on the type of functional layer 22. For example, when the functional layer 22 is a decorative layer, the thickness is preferably 0.1 to 20 μm, and more preferably 0.5 to 10 μm. When the functional layer 22 is an adhesive layer, the thickness is preferably 0.5 to 150 μm, and more preferably 1 to 80 μm.

2(b) and 2(c), the functional layer 22 is formed by applying a liquid functional layer composition containing functional components according to the type of functional layer to the surface of the polyurethane resin layer 21 formed by the above polyurethane resin layer formation process, followed by drying and curing (functional layer formation process). The functional layer composition is a composition containing functional components such as pigments and inks, and resin components. Examples of the resin components contained in the functional layer composition include acrylic resins, urethane resins, fluorine resins, silicone resins, polyester resins, polycarbonate resins, melamine resins, epoxy resins, olefin resins, polystyrene resins, cellulose resins, phenol resins, polyvinyl resins, polyamide resins, polyimide resins, and chlorinated rubber. The resin components may be the same as the polyurethane resin constituting the polyurethane resin layer 21.

The functional layer composition is preferably compatible with component D. In this case, when the functional layer 22 is formed on the surface of the polyurethane resin layer 21, component D contained in the polyurethane resin layer 21 is more likely to diffuse into the functional layer 22.

The method of applying and drying the functional layer composition is the same as that for the resin composition described above. The functional layer 22 may also be formed by other methods, for example, by laminating and adhering a layer that has been previously formed using the functional layer composition onto the surface of the polyurethane resin layer 21.

(How to use the laminated film)
The laminated film F is used by being attached to the surface of an article for the purpose of protecting the surface of the article, adding decoration to the surface of the article, etc. Examples of articles to which the laminated film F is attached include vehicles, home appliances, mobile terminals, personal computers, furniture, cosmetic containers, sporting goods, tableware, etc. Specific examples of the attachment site in a vehicle include the surfaces of three-dimensional molded products such as exterior panels and exterior/interior parts of the vehicle, more specifically, the surfaces of bonnets, light frames, grilles, bumpers, skirts, roofs, fenders, doors, handlebars, steps, mirrors, trunk lids, license plates, wheels, mufflers, door trims, instrument panels, cup holders, audio parts, console boxes, shift lever grips, and peripheral parts that constitute these.

Figure 3 shows an example of how to use the laminate film F. First, the surface of the laminate film F on the side of the functional layer 22 faces the article 30, and the laminate film F is attached to the surface of the article 30 with no gap between them (attaching process). Then, the release film 10 is peeled off from the laminate film F attached to the article 30 (peeling process), thereby obtaining a film-attached article 31 in which the main film 20 is attached to the surface of the article 30. Note that since the polyurethane resin layer 21 has excellent flexibility, it can be easily deformed to fit the three-dimensional shape of the surface of the article 30, even if the surface of the article 30 has a three-dimensional shape.

The method of attaching the main film 20 of the laminated film F to the article 30 is not limited to the above method. For example, the release film 10 may be peeled off from the laminated film F before attaching the laminated film F to the article 30, that is, a peeling process may be performed before the attachment process. The laminated film F may also be applied to out-mold molding methods other than those described above, such as vacuum molding, overlay molding, hot stamping, and hydraulic transfer. The laminated film F may also be applied to in-mold molding methods in which the main film 20 of the laminated film F is attached to the surface of the article 30 at the same time as the article 30 is molded, such as a film in-mold decoration method and an in-mold labeling method.

Next, the effects of this embodiment will be described.
(1) The laminated film F comprises a release film 10 and a main film 20 releasably adhered to a first main surface 10a of the release film 10. The main film 20 comprises a polyurethane resin layer 21 adhered to the release film 10, and a functional layer 22 made of a functional component formed on the surface of the polyurethane resin layer 21 opposite to the release film 10. The polyurethane resin layer 21 is a thermoset of a resin composition containing at least one of (A) a (meth)acrylic resin having a hydroxy group and (B) a polyol, (C) a polyfunctional isocyanate, and (D) a modified polydialkylsiloxane compound, and the peak top temperature is −80° C. or higher.

According to the above configuration, the polyurethane resin layer 21 having scratch recovery properties contains a modified polydialkylsiloxane compound (D). This makes it possible to obtain a polyurethane resin layer 21 that has peelable adhesion to the release film 10 provided on one surface, while having adhesion to the functional layer 22 provided on the other surface such that it does not easily peel off during formation, etc. As a result, it becomes possible to use films other than low-adhesion release films, such as films made of low-adhesion materials or films whose surfaces have been treated with a release treatment that reduces adhesion, and this makes it possible to suppress a decrease in the freedom of choice of release films.

By including the (D) modified polydialkylsiloxane compound in the polyurethane resin layer 21, when the polyurethane resin layer 21 is formed by coating, poor appearance such as poor leveling and cissing is less likely to occur. This makes it possible to form a polyurethane resin layer 21 with excellent surface appearance.

The mechanism by which the above effect (1) is obtained can be assumed to be as follows.
When the polyurethane resin layer 21 is formed on the release film 10, the modified polydialkylsiloxane compound (D) is oriented to form a coating at the interface between the release film 10 and the polyurethane resin layer 21. It is believed that this coating inhibits excessive adhesion between the release film 10 and the polyurethane resin layer 21, resulting in the polyurethane resin layer 21 having adhesiveness that allows it to be peeled off from the release film 10.

On the other hand, when forming the functional layer 22 on the polyurethane resin layer 21, the modified polydialkylsiloxane compound (D) does not remain at the interface between the polyurethane resin layer 21 and the functional layer 22 but diffuses into the functional layer 22, so it is believed that the modified polydialkylsiloxane compound (D) does not inhibit adhesion between the polyurethane resin layer 21 and the functional layer 22.

(2) The polyurethane resin layer 21 has a peak top temperature of 90° C. or less.
According to the above-mentioned configuration, the polyurethane resin layer 21 functions as a protective layer having excellent flexibility and scratch recovery. The flexible polyurethane resin layer 21 has a property of having particularly high adhesion to the release film 10, and therefore the effect of (1) above by containing the modified polydialkylsiloxane compound (D) can be obtained more significantly.

(3) The resin composition preferably contains both (A) a (meth)acrylic resin having a hydroxy group and (B) a polyol.
According to the above-mentioned configuration, a portion with a low cross-linking density and a portion with a high cross-linking density are formed during curing, thereby obtaining a polyurethane resin layer 21 having a sparsely and densely cross-linked structure. This provides the polyurethane resin layer 21 with an appropriate toughness, and remarkably improves the scratch recovery of the polyurethane resin layer 21.

(4) It is preferable that the surface free energy of the first main surface 10a of the release film 10 is 20 to 50 mN/m.
According to the above-mentioned configuration, the effect of preventing occurrence of poor appearance such as poor leveling and cissing when forming the polyurethane resin layer 21 by coating, as described in (1), can be more significantly obtained. In addition, the effect of suppressing breakage of the main film 20 and peeling failure when peeling the release film 10 from the main film 20 can be obtained.

(5) The first main surface 10 a of the release film 10 is a surface that has been subjected to a release treatment using a release agent 11 .
According to the above-mentioned configuration, the surface free energy of the first main surface 10a of the release film 10 can be easily adjusted to a specific range.

(6) The release agent 11 is preferably a non-silicone release agent.
In the case where the first main surface 10a of the release film 10 is subjected to a release treatment using the release agent 11, when the above-mentioned resin composition is applied to the first main surface 10a of the release film 10 to form the polyurethane resin layer 21, the release agent 11 may migrate from the release film 10 side to the polyurethane resin layer 21. In this case, if the release agent 11 is a silicone-based release agent that is a silicone-containing compound with low surface free energy, the surface free energy of not only the surface of the polyurethane resin layer 21 on the release film 10 side, but also the surface opposite the release film 10 is greatly reduced. Therefore, when forming the functional layer 22 on the surface of the polyurethane resin layer 21 opposite the release film 10, problems such as repelling or poor adhesion may occur. When a non-silicone-based release agent is used as the release agent 11, such problems can be reduced.

This embodiment can be modified as follows: This embodiment and the following modifications can be combined with each other to the extent that no technical contradiction occurs.
The main body film 20 may include one or more other layers on the surface of the functional layer 22 opposite the polyurethane resin layer 21. For example, the main body film 20 may have a three-layer structure in which the polyurethane resin layer 21, a decorative layer, and an adhesive layer are laminated in this order from the polyurethane resin layer 21 side. In this case, the decorative layer adhered to the polyurethane resin layer 21 becomes the functional layer 22, and the adhesive layer adhered to the functional layer 22 becomes the other layer.

The laminated film F may have a structure in which the release film 10 is adhered to both sides of the main film 20. In this case, the same release film 10 may be adhered to both sides of the main film 20, or different release films 10 may be adhered to each side. In addition, the laminated film F in which the release film 10 is adhered to both sides of the main film 20 can be used by further forming a functional layer 22, such as an anti-reflection layer, on the exposed surface of the polyurethane resin layer 21 after peeling off the release film 10 adhered to the polyurethane resin layer 21.

The laminated film F may be a processing film in which the functional layer 22 is omitted (as shown in FIG. 2(b)), and a functional layer 22 such as an anti-reflection layer is formed on the surface of the polyurethane resin layer 21 opposite the release film 10, or on the surface of the polyurethane resin layer 21 after one release film 10 is peeled off when the release film 10 is attached to both sides of the polyurethane resin layer 21. In this case, the wetting tension of the surface of the polyurethane resin layer 21 on which the functional layer 22 is formed is preferably, for example, 30 to 65 mN/m.

The problem of repelling or poor adhesion caused by the release agent 11 of the release film 10 when forming the functional layer 22, as described in section (6) above, also occurs when forming the functional layer 22 on the surface of the polyurethane resin layer 21 to which the release film 10 was adhered. Therefore, when the release film 10 is attached to both sides of the polyurethane resin layer 21, it is preferable that the release agent 11 used in the release treatment is a non-silicone release agent, even for the release film 10 attached to the surface of the polyurethane resin layer 21 on which the functional layer 22 is formed.

The above embodiment will be described in more detail below with reference to examples and comparative examples, although the present invention is not limited thereto.
(Preparation of Component A)
A four-neck flask equipped with a thermometer, a thermostat, a stirring device, a reflux condenser, and a dropping device was prepared. 100 parts by mass of methyl ethyl ketone was charged into this flask and heated to 79°C with stirring. Next, a mixture of (meth)acrylic monomers in the ratio (unit: parts by mass) shown in Table 6 and 2 parts by mass of 2,2-azobis(2-methylbutyronitrile) (ABN-E manufactured by Japan Finechem Co., Ltd.) as a polymerization initiator was continuously dropped into the flask from the dropping funnel over 2 hours. As the (meth)acrylic monomers, a mixture of the monomers shown in Table 1 in the ratio (unit: parts by mass) shown in Tables 5 to 7 was used.

After the dropwise addition was completed, the mixture was stirred at 79°C for an additional 3 hours to react the remaining monomers. Heating was then stopped and the mixture was cooled to room temperature to obtain a composition (solid content ratio 50% by mass) containing a (meth)acrylic resin having a hydroxyl group, which is component (A).

Details of the (meth)acrylic monomers used in the test are shown in Table 1.

(Synthesis of component D)
Polyether-modified polydialkylsiloxanes were synthesized as modified polydialkylsiloxane compounds D1 to D3, which are component D. The polyether-modified polydialkylsiloxanes were synthesized by addition reaction of methylhydrogenpolysiloxane and polyoxyethylene monoallyl ether in the presence of a platinum catalyst. For comparison, alkyl-modified polydialkylsiloxane E-1 and aralkyl-modified polydialkylsiloxane E-2, which are other modified polydialkylsiloxanes not corresponding to component D, were also synthesized.

As the methylhydrogenpolysiloxane, the following methylhydrogenpolysiloxanes S-1 to S-3 were used.
S-1: Methylhydrogenpolysiloxane in which m = 8, n = 8 in the above formula (8) S-2: Methylhydrogenpolysiloxane in which m = 12, n = 4 in the above formula (8) S-3: Methylhydrogenpolysiloxane in which m = 4, n = 12 in the above formula (8) As the polyoxyethylene monoallyl ether, polyoxyethylene monoallyl ethers O-1 to O-2 represented by the following average composition formula were used. Polyoxyethylene monoallyl ethers O-1 to O-2 were synthesized by known synthesis methods.

O-1: CH ₂ =C(CH ₃ )CH ₂ CH ₂ -O-(CH ₂ CH ₂ O) ₉ -CH ₃
O-2: CH ₂ =C(CH ₃ )CH ₂ CH ₂ -O-(CH ₂ CH ₂ O) ₂₂ -CH ₃
<Synthesis Example 1>
Into a four-neck flask equipped with a reflux condenser, a stirrer, and a dropping funnel, polyoxyethylene monoallyl ether O-1 (119 parts by mass), isopropanol (100 parts by mass), and chloroplatinic acid having a platinum content of 1% were added. An isopropanol solution (0.2 parts by mass) and a 1% methanol solution of sodium acetate (3 parts by mass) were added, and the temperature was raised to reflux conditions for the solvent under a nitrogen stream. Next, methylhydrogenpolysiloxane S was added from the dropping funnel. The mixture was cooled and filtered using a filter aid. The mixture was then kept at 120° C. and 10 Torr for 1 hour to remove the solvent and the The other low boiling points were completely removed to obtain a modified polydialkylsiloxane compound D-1.

<Synthesis Example 2>
A modified polydialkylsiloxane compound D-2 was obtained in the same manner as in Synthesis Example 1, except that polyoxyethylene monoallyl ether O-1 (119 parts by mass) was changed to polyoxyethylene monoallyl ether O-2 (128.2 parts by mass) and that methylhydrogenpolysiloxane S-1 (37 parts by mass) was changed to methylhydrogenpolysiloxane S-2 (38.7 parts by mass).

<Synthesis Example 3>
A modified polydialkylsiloxane compound D-3 was obtained in the same manner as in Synthesis Example 1, except that polyoxyethylene monoallyl ether O-1 (119 parts by mass) was changed to polyoxyethylene monoallyl ether O-1 (89.4 parts by mass) and 1-octene (20.1 parts by mass), and that methylhydrogenpolysiloxane S-1 (37 parts by mass) was changed to methylhydrogenpolysiloxane S-3 (35.4 parts by mass).

<Synthesis Example 4>
An alkyl-modified polydialkylsiloxane E-1 was obtained in the same manner as in Synthesis Example 1, except that polyoxyethylene monoallyl ether O-1 (119 parts by mass) was changed to 1-octene (26.9 parts by mass).

<Synthesis Example 5>
An aralkyl-modified polydialkylsiloxane E-2 was obtained in the same manner as in Synthesis Example 1, except that polyoxyethylene monoallyl ether O-1 (119 parts by mass) was changed to α-methylstyrene (28.3 parts by mass).

(Preparation of Resin Composition)
Composition A1 and one or both of polyols as component B, polyfunctional isocyanate as component C, and any one of modified polydialkylsiloxane compounds as component D were mixed in the ratios (units: parts by mass) shown in Tables 6 to 9, and methyl ethyl ketone was further added to obtain a resin composition having a solid content ratio of 65% by mass. As component D, synthesized modified polydialkylsiloxane compounds D-1 to D-3 and a commercially available product were used. In addition, in Comparative Examples 1 to 3, the modified polydialkylsiloxane compound as component D was not contained, and in Comparative Examples 1 and 2, other modified polydialkylsiloxanes were mixed.

Details of the polyols, polyfunctional isocyanates, modified polydialkylsiloxane compounds, and other modified polydialkylsiloxanes used in the tests are shown in Tables 2 to 4. The values in the "NCO%" column in Table 3 indicate the percentage content when the total solid content is taken as 100%, and the values in parentheses indicate the percentage content when the total solid content and solvent is taken as 100%.

(Formation of polyurethane resin layer)
The resin composition prepared above was applied to the first main surface of each of the release films using a bar coater so that the thickness of the cured film was the value shown in Tables 6 to 9, and the film was left to stand at room temperature for 1 minute. The film was then dried by heating at 140°C for 2 minutes using a hot air dryer, and then left in a dryer at 40°C for 72 hours. This resulted in the formation of a polyurethane resin layer of any desired thickness. This resulted in the laminated films of the examples and comparative examples in which the polyurethane resin layer was adhered to the surface of the release film. Details of the release films used in the test are as shown in Table 5.

<Measurement of Glass Transition Temperature of Polyurethane Resin Layer>
The polyurethane resin layer obtained by peeling the release film from the laminated film of each of the Examples and Comparative Examples was cut into test pieces with a width of 5 mm and a length of 50 mm. Using these test pieces, the peak top temperature of the loss tangent (tan δ) was measured under the following conditions. The results are shown in Tables 6 to 9.

Apparatus: Dynamic viscoelasticity measuring device RSA-G2 (manufactured by TA Instruments)
Measurement mode: Non-resonant forced vibration method Temperature rise rate: 5.0°C/min
Measurement interval: 12/min
Frequency: 1.0Hz
Distance between jigs: 20 mm
Temperature range: -120 to 250°C
(Evaluation of Examples and Comparative Examples)
The obtained laminated films of the Examples and Comparative Examples were evaluated as follows.

<Evaluation of Appearance of Polyurethane Resin Layer>
The surface of the formed polyurethane resin layer was visually observed and the appearance was evaluated based on the following criteria. The results are shown in Tables 6 to 9.

⊚: No appearance defects such as poor leveling or repelling.
◯: Almost no appearance defects such as poor leveling or cissing.
Δ: Partial leveling failure, repelling, and other appearance failures are observed.

×: Overall leveling failure, appearance failure such as repelling, etc. is observed, or a resin layer cannot be formed due to leveling failure, repelling, etc.
<Scratch Resistance of Polyurethane Resin Layer>
Under an atmosphere of 25°C temperature and 60% RH relative humidity, a brass brush (three rows of wooden-handled brass brush) was applied to the surface of the polyurethane resin layer of the laminated film of the examples and comparative examples, and scratched by 10 reciprocations under a load of 500 g. After that, the film was left for 1 hour under the first condition of 60% RH relative humidity and 25°C temperature, and the time until the scratch on the surface of the polyurethane resin layer was restored was measured. If the scratch was not restored after 1 hour, the condition was changed to the second condition of 60% RH relative humidity and 80°C temperature, and the film was left for 1 hour, and the time until the scratch was restored was further measured. Then, the scratch restoration property of the polyurethane resin layer was evaluated according to the following criteria. The results are shown in Tables 6 to 8.

⊚: The damage was repaired in less than one minute under the first condition.
◯: The scratch is repaired in 1 minute or more and less than 10 minutes under the first condition.
□: Under the first condition, the scratch is repaired within 10 minutes to less than 1 hour.

△: The damage was repaired within 1 hour after changing to the second condition.
×: The damage is not repaired within 1 hour after changing to the second condition.
<Measurement of Wet Tension of Polyurethane Resin Layer>
The wet tension of the surface of the polyurethane resin layer was measured using a mixture for wet tension testing (manufactured by Kanto Chemical Co., Ltd.) according to a method in accordance with JIS K6768. The results are shown in Tables 6 to 9.

<Measurement of Peel Strength Between Release Film and Polyurethane Resin Layer>
The laminated films of the Examples and Comparative Examples were used as test pieces, and peel strength (mN/25 mm) was measured using a precision universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation) in accordance with a method in accordance with JIS Z0237 under conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees. Of the measured values obtained, the average value of the peel force at peel distances of 20 mm to 70 mm was taken as the peel strength. The peel strength was also evaluated according to the following criteria. The results are shown in Tables 6 to 9.

◎: 1200mN/25mm or less.
○: More than 1200 mN/25 mm and less than 2400 mN/25 mm.
□: More than 2,400 mN/25 mm and less than 3,000 mN/25 mm.

△: More than 3000 mN/25 mm and 4000 mN/25 mm or less.
×: Exceeds 4000 mN/25 mm.
<Evaluation of the Appearance of the Functional Layer>
A polyurethane-based gravure ink having a liquid surface tension of 19.0 mN/m was applied to the surface of the polyurethane resin layer of the laminated film of the examples and comparative examples by a bar coater so that the non-volatile content was 28% and the liquid surface tension was 1 to 2 μm after drying, and the ink was dried at 80° C. for 10 minutes by a dryer to form a functional layer (decorative layer) on the surface of the polyurethane resin layer. The surface of the formed functional layer was visually observed, and the appearance was evaluated based on the following criteria. The results are shown in Tables 6 to 8. The liquid surface tension of the polyurethane-based gravure ink was measured by the Wilhelmy method using a surface tensiometer (DY-300 manufactured by Kyowa Interface Science Co., Ltd.).

⊚: No appearance defects such as poor leveling or repelling.
◯: Almost no appearance defects such as poor leveling or cissing.
Δ: Partial leveling failure, repelling, and other appearance failures are observed.

×: Overall leveling failure, appearance failure such as repelling, etc. is observed, or a resin layer cannot be formed due to leveling failure, repelling, etc.
<Evaluation of Adhesion Between Polyurethane Resin Layer and Functional Layer>
The functional layers formed in the above evaluation of the appearance of the functional layers were subjected to an adhesion test (cross-cut method) according to JIS K5600, and the adhesion was evaluated based on the following criteria. The results are shown in Tables 6 to 8. Note that cellophane tape (Cellotape (registered trademark) CT405AP manufactured by Nichiban Co., Ltd.) was used for the test.

⊚: No peeling.
○: Peeling occurred in less than 5% of the total area.
□: Peeling occurs in less than 10% of the total area.

Δ: Peeling occurred in less than 20% of the total area.
×: Peeling occurred in 20% or more of the total area.

As shown in Tables 6 to 9, in each of the Examples in which the polyurethane resin layer contained the modified polydialkylsiloxane compound, which is the component D, all evaluations except for the evaluation of scratch recovery were "◎" to "△". On the other hand, in Comparative Example 1 in which alkyl-modified polydialkylsiloxane E-1 was used instead of the component D, and Comparative Example 2 in which aralkyl-modified polydialkylsiloxane E-2 was used, the evaluation of the appearance of the functional layer and the evaluation of the adhesion between the polyurethane resin layer and the functional layer were "x". In addition, in Comparative Example 3 in which neither the component D nor other modified polydialkylsiloxanes were contained, the evaluation of the appearance of the polyurethane resin layer and the evaluation of the peel strength between the polyurethane resin layer and the release film were "x".

These results show that by incorporating a modified polydialkylsiloxane compound, which is component D, into the polyurethane resin layer, it is possible to obtain the effect of reducing the adhesion of the polyurethane resin layer to the release film while ensuring high adhesion of the polyurethane resin layer to the functional layer. It is also clear that this effect is unique to the specific modified polydialkylsiloxane compound.

In addition, in Comparative Example 4, in which the above-mentioned peak top temperature of the polyurethane resin layer was lower than -80°C, the peel strength between the polyurethane resin layer and the release film was evaluated as "X". From this result, it can be seen that in order to reduce the peel strength between the polyurethane resin layer and the release film, the above-mentioned peak top temperature of the polyurethane resin layer needs to be -80°C or higher.

In addition, in Example 21, in which the above-mentioned peak top temperature of the polyurethane resin layer exceeded 90°C, the scratch recovery was rated as "X", and scratch recovery was not achieved. On the other hand, in other Examples in which the above-mentioned peak top temperature was 90°C or less, scratch recovery was rated as "△" to "◎", and scratch recovery was achieved.

Furthermore, the results of Examples 53 to 58 show that when a release film that has been treated with a release agent is used, the peel strength between the polyurethane resin layer and the release film decreases and the peelability improves. In particular, when the release agent is a non-silicone release agent, the peelability between the polyurethane resin layer and the release film improves without reducing the adhesion between the polyurethane resin layer and the functional layer.

Although details are omitted, tests were conducted for Examples 11 and 15 in which an adhesive layer containing an acrylic adhesive was formed as the functional layer. In this case as well, the effect of reducing the adhesion of the polyurethane resin layer to the release film was obtained while maintaining high adhesion of the polyurethane resin layer to the functional layer.

Although details are omitted, in Example 11, a laminated film was prepared in which a second release film was attached to the surface of the polyurethane resin layer opposite the release film, and a test was conducted in which the second release film was peeled off from this laminated film to form a decorative layer or adhesive layer as a functional layer on the surface of the exposed polyurethane resin layer. As a result, in this case too, high adhesion of the polyurethane resin layer to the functional layer was obtained.

F...Laminated film 10...Release film 10a...First main surface 11...Release agent 20...Main film 21...Polyurethane resin layer 22...Functional layer 30...Article 31...Article with film

Claims (9)

A release film and a main body film releasably adhered to a first main surface of the release film,
The main body film is a processing film having a polyurethane resin layer adhered to the release film, and is used by forming a functional layer made of a functional component on a surface of the polyurethane resin layer,
the polyurethane resin layer is a thermoset product of a resin composition containing at least one of (A) a (meth)acrylic resin having a hydroxy group and (B) a polyol, (C) a polyfunctional isocyanate, and (D) a modified polydialkylsiloxane compound;
The modified polydialkylsiloxane compound (D) is a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure,
the polyurethane resin layer has a peak top temperature of loss tangent of −80° C. or higher, the peak top temperature being obtained by dynamic viscoelasticity measurement at a frequency of 1.0 Hz and a temperature range of −120 to 250° C.;
The laminated film , wherein the polyol (B) has a hydroxyl value of 80 to 600 mgKOH/g . A release film and a main body film releasably adhered to a first main surface of the release film,
the main body film comprises a polyurethane resin layer adhered to the release film, and a functional layer made of a functional component formed on a surface of the polyurethane resin layer opposite to the release film,
the polyurethane resin layer is a thermoset product of a resin composition containing at least one of (A) a (meth)acrylic resin having a hydroxy group and (B) a polyol, (C) a polyfunctional isocyanate, and (D) a modified polydialkylsiloxane compound;
The modified polydialkylsiloxane compound (D) is a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure,
the polyurethane resin layer has a peak top temperature of loss tangent of −80° C. or higher, the peak top temperature being obtained by dynamic viscoelasticity measurement at a frequency of 1.0 Hz and a temperature range of −120 to 250° C.;
The laminated film , wherein the polyol (B) has a hydroxyl value of 80 to 600 mgKOH/g . The laminated film according to claim 1 or 2, wherein the polyurethane resin layer has a peak top temperature of 90°C or less. The laminated film according to any one of claims 1 to 3, wherein the surface free energy of the first main surface of the release film is 20 to 50 mN/m. The laminated film according to claim 4, wherein the first main surface of the release film is a surface that has been subjected to a release treatment using a release agent. The laminated film according to claim 5, wherein the release agent is a non-silicone release agent. A method for producing the laminated film according to claim 2,
a polyurethane resin layer forming step of forming the polyurethane resin layer on a first main surface of the release film;
and forming a functional layer on the surface of the polyurethane resin layer, the functional layer being made of a functional component.
the polyurethane resin layer forming step is a step of forming the polyurethane resin layer by thermally curing a resin composition containing at least one of (A) a (meth)acrylic resin having a hydroxy group and (B) a polyol, (C) a polyfunctional isocyanate, and (D) a modified polydialkylsiloxane compound;
The modified polydialkylsiloxane compound (D) is a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure,
The polyurethane resin layer has a peak top temperature of loss tangent of -80°C or higher, as determined by dynamic viscoelasticity measurement at a frequency of 1.0 Hz and a temperature range of -120 to 250°C. A method for producing an article with a film, comprising the steps of:
A lamination step of laminating a functional layer comprising a functional component on a surface of the polyurethane resin layer of the laminate film according to claim 1;
A method for manufacturing an article with a film, comprising a peeling step of peeling the release film from the laminate film before or after attaching the laminate film having the functional layer laminated thereon to an article. A resin composition used as a raw material for the polyurethane resin layer of the laminate film according to any one of claims 1 to 6,
(A) at least one of a (meth)acrylic resin having a hydroxy group and (B) a polyol, (C) a polyfunctional isocyanate, and (D) a modified polydialkylsiloxane compound,
The (A) (meth)acrylic resin having a hydroxy group has a glass transition temperature of −75 to 100° C. and a hydroxyl value of 20 to 150 mgKOH/g,
the (B) polyol is a polyol selected from the group consisting of polylactone polyols, polycarbonate polyols, polyester polyols, and polyether polyols, has a number average molecular weight of 100 to 3,000, and has two or more hydroxy groups in one molecule;
The polyfunctional isocyanate (C) has two or more isocyanate groups in one molecule,
The modified polydialkylsiloxane compound (D) is a compound having a polydialkylsiloxane structure and a modified structure selected from the group consisting of a polyester chain and a polyether chain bonded to the polydialkylsiloxane structure.