JP3261182B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is mainly applied to the surface of a plastic film such as polyvinyl chloride or polyester to impart water repellency, lubricity, mold release, heat resistance, etc. to the film surface. It concerns the coating composition used.

[0002]

2. Description of the Related Art For example, polyesters used for the purpose of imparting dustproofness, barrier properties, peelability, etc. to soft polyvinyl chloride for agricultural use, dustproof polyvinyl chloride, etc., and as a base material for magnetic tapes, thermal transfer ribbons and the like. Polyethylene terephthalate (PET) and polyethylene naphthalate (PE)
A coating treatment is performed to impart water repellency, lubricity, mold releasability, heat resistance and the like to the front or back surface of the plastic film substrate such as N).

Conventionally, attempts have been made to obtain a graft copolymer using a silicon macromonomer for use in such a surface coating treatment of a plastic film.

[0004]

However, for example, it is difficult to sufficiently satisfy the heat resistance required for the backside coating agent of the thermal transfer ribbon, and even if the heat resistance is satisfied, the film strength and the adhesion are low. Often inferior.

[0005]

According to the present invention, as a means for solving the above-mentioned conventional problems , a radical polymerizable compound is added to the terminal.
A silicon macromonomer A having a vinyl group and a vinyl monomer B represented by the following structural formula

Embedded image Here, R is H or CH ₃ . If consists of a graft copolymer of the silicon macromonomer A and vinyl monomer B copolymerizable with other vinyl monomer C, wherein
Graft copolymer is a trunk polymer composed of vinyl monomer B
And a coating composition comprising a branch polymer composed of silicon macromonomer A , wherein the coating composition has heat resistance, film strength, without impairing the water repellency, lubricity and mold release properties of silicon. It has excellent properties such as adhesion.

The present invention will be described in detail below. A [divorced macromonomer A] silicon macromonomer having a radically polymerizable vinyl group at the terminal and is used Resid silicon macromonomer A in the present invention, such silicone macromonomer is e.g. polydialkylsiloxanes end of Α-β unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid and crotonic acid are introduced by esterification using OH groups, and acrylic such as methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate are transesterified. Mono- or methacrylic esters of polydialkylsiloxanes obtained by introducing esters and methacrylic esters, or vinyl monomers having OH groups such as allyl alcohol are introduced by etherification. Monoallyl ethers of polydialkylsiloxane and the like is that. Usually, the polydialkylsiloxane has a molecular weight of 100
Those having about 0 to 50,000 and having an alkyl group having a lower alkyl group having 4 or less carbon atoms are used.

[Vinyl monomer B] The vinyl monomer B used in the present invention comprises:

Embedded image Here, R is H or CH ₃ . Wherein the vinyl monomer B includes acryloyl morpholine and methacryloyl morpholine.

[Other Vinyl Monomer C] The other vinyl monomer C used in the present invention can be copolymerized with the above silicon macromonomer A and the above phosphoric acid group-containing vinyl monomer B. Yes, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate,
Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether,
Ethyl vinyl ether, n-propyl vinyl ether, n-
Butyl vinyl ether, iso-butyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol, glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, citraconic acid, acrylamide, methacryl There are vinyl monomers such as amide, N-methylolacrylamide, N-methylolmethacrylamide, dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate.

[Production of Graft Copolymer] The graft copolymer of the present invention is usually produced by solution polymerization. As the solvent used in the solution polymerization, usually, aromatic hydrocarbon solvents such as toluene and xylene, acetone, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone,
Ester solvents such as ethyl acetate and butyl acetate, and alcohol solvents such as ethanol and isopropyl alcohol are used as one kind or a mixture of two or more kinds. Examples of the polymerization initiator used in the solution polymerization include benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, azobisisobutyronitrile,
There are oil-soluble initiators such as azobisvaleronitrile.

As the monomer formulation, one or more silicon macromonomer A is usually about 10 to 50% by weight, vinyl monomer B is about 5 to 80% by weight, vinyl monomer C is one or more. Two or more of them are about 10 to 85% by weight.

[Coating] The coating composition of the present invention thus obtained is applied to a substrate such as a PVC film or a PET film by a usual coating method such as spraying, roll coater, flow coater and spin coating. It is applied in a thickness of 1 μm or less. The coating film obtained by the above coating can be dried by drying at room temperature, but is usually subjected to forced drying at 100 to 120 ° C. for about 1 to 5 minutes.

[0012]

According to the present invention, in the graft copolymerization,
The branch polymer of the polydialkylsiloxane chain and the backbone polymer composed of the component of (meth) acryloylmorpholine as the monomer B are easily microphase separated, and the effect of physical crosslinking is large. Therefore, the properties of the trunk polymer and the branch polymer are effectively exhibited. That is, the water repellency, lubricity, and releasability are improved by the polydialkylsiloxane chain, and the adhesion to the substrate and the film strength are improved by the branched polymer. In addition, a large molecular cohesion energy derived from the molecular structure of (meth) acryloylmorpholine increases the melting point of the polymer and improves heat resistance.

[0013]

【Example】

Example 1 Methyl ethyl ketone 2 was placed in a 1-liter flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube.
After adding 00 parts by weight (hereinafter simply referred to as “parts”) and bubbling with nitrogen gas for 30 minutes, the temperature is raised to 80 ° C. To a separately prepared dropping funnel, 50 parts of methyl methacrylate, 20 parts of acryloylmorpholine, AK-30
A liquid mixture of 30 parts (trade name: silicon macromonomer, molecular weight: about 30,000, manufactured by Toagosei Chemical Industry Co., Ltd.) and 0.5 part of azobisisobutyronitrile is added and dropped over 2 hours. One hour later, a solution obtained by dissolving 0.1 part of azobisisobutyronitrile in 30 parts of methyl ethyl ketone was added and reacted at 80 ° C. for 5 hours. Thus, a milky white resin liquid having a solid content of 30.1% by weight was obtained. This is designated as resin A.

Example 2 In the same apparatus as in Example 1, 40 parts of methyl methacrylate and 20 parts of acryloylmorpholine 20 were used.
The polymerization was carried out in the same manner as in Example 1 except that 10 parts by weight, 10 parts by weight of methacrylic acid, and 30 parts by FM0725 (trade name: polydimethylsiloxane having a terminal methacryloxy group, molecular weight: 10,000, manufactured by Chisso Corporation). Thus, a milky resin liquid having a solid content of 30% by weight was obtained. This is called resin B.

Example 3 In the same apparatus as in Example 1, 10 parts of styrene, 80 parts of acryloylmorpholine, AK-3
0 to 10 parts, and the polymerization solvent is isopropyl alcohol 2
Polymerization was carried out in the same manner as in Example 1 except that the amount was changed to 00 parts. Thus, the solid content is 30.3% by weight.
To obtain a milky white resin liquid. This is called resin C.

Comparative Example 1 In the same apparatus as in Example 1, methyl methacrylate 60 parts, methacrylic acid 10 parts, AK-
30 as 30 parts, and the polymerization solvent is methyl ethyl ketone 20
Polymerization was carried out in the same manner as in Example 1 except that the amount was 0 parts. The obtained resin solution was milky white and had a solid content of 30.
It was 5% by weight. This is designated as resin D.

Comparative Example 2 In the same apparatus as in Example 1, 50 parts of methyl methacrylate, 20 parts of methacrylic acid, FM0
725 to 30 parts, and the polymerization solvent is methyl ethyl ketone 2
Polymerization was carried out in the same manner as in Example 1 except that the amount was changed to 00 parts. The resin solution obtained is milky white and has a solid content of 30.
% By weight. This is designated as resin E.

Each of the copolymers A, B, C, D and E obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was adjusted with methyl ethyl ketone so that the solid content was 5% by weight, and the PET film was obtained. The above samples were each coated with a roll coater so as to have a thickness of 0.5 μm.
After forced drying for 5 minutes, a test for physical properties was performed. Table 1 shows the results.

[0019]

[Table 1] Test method Tg: Theoretical Tg (glass transition point) by Fox equation Adhesion: Cross cut cellophane tape peeling test Dynamic friction coefficient: HEIDON type friction measuring device Film strength: Scratch tester manufactured by Resca Corporation Ts: Thermomechanical analysis manufactured by Seiko Electronics Thermal softening point by equipment

According to Table 1, in Examples 1, 2, and 3 (resins A, B, and C) using the coating composition of the present invention, good lubricity (dynamic friction coefficient), adhesion, film strength, and heat Softening point (T
g) is obtained, but Comparative Examples 1 and 2 (resins D and E) in which acryloylmorpholine is not used as the base polymer are inferior in adhesion, film strength and heat softening point. This result does not depend on Tg, and the one having a high Tg has a higher thermal softening temperature (T
This does not mean that s) increases, but the effect is exhibited in a copolymer into which acryloylmorpholine is introduced.

[0021]

Accordingly, in the present invention, a coating composition which satisfies the inherent lubricity, water repellency and releasability of silicon and which is excellent in adhesion to plastic films and the like, heat resistance and film strength can be obtained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Susumu Kawakami, No. 8-3, Ninocho, Mizuho-ku, Nagoya, Aichi Prefecture Inside Natco Paint Co., Ltd. (72) Hironori Hata No. 8, Ninocho, Mizuho-ku, Nagoya, Aichi Prefecture No. 3 Inside Natco Paint Co., Ltd. (72) Inventor Keiji Taniguchi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Shigeyuki Harada 1-3-6 Nakamagome, Ota-ku, Tokyo No. Ricoh Co., Ltd. (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 183/10

Claims (1)

(57) [Claims] 1. A silicon macromonomer A having a radically polymerizable vinyl group at a terminal, and a vinyl monomer B represented by the following structural formula: Here, R is H or CH ₃ . If, Ri Do and a graft copolymer of the silicon macromonomer A and vinyl monomer B copolymerizable with other vinyl monomer C, wherein
Graft copolymer is a trunk polymer composed of vinyl monomer B
Or a branch polymer composed of silicon macromonomer A
Coating composition characterized Rana Rukoto