JP3132835B2 - Method for producing coated vinyl chloride resin sheet and coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates, about the coated preparation and the coating composition of the vinyl chloride resin sheet.

[0002]

Conventionally, with respect to vinyl chloride resin sheet surface to prevent oozing of the plasticizer of the component, and while reducing the adhesion of dirt, for the purpose of facilitating the removal of embedded contamination, Processing such as lamination of a vinylidene fluoride resin film and coating of an acrylic resin has been performed.
However, the laminating of a vinylidene fluoride resin film or the like is limited in free processability , for example, the size of the underlying vinyl chloride resin film is regulated.

[0003] The coating of an acrylic resin or the like is of a lacquer type in which a film is formed mainly by volatilization and drying of a solvent which does not involve a crosslinking reaction, so that the productivity is good . Only
And, not completely prevent out penetrates the plasticizer from the vinyl chloride resin sheet is an object sufficiently, or hanging fouling Re yet ease attachment.
Removal of attached dirt, for example, performed in a solvent coating also had dissolved, there is a problem in terms of performance.

[0004]

[To be solved problem of the invention An object of the present invention is Attempting to solve the above-mentioned drawbacks the prior art has had. In other words, the performance is comparable to that of a vinylidene fluoride resin film laminated product , and is the same as that of a coating such as an acrylic resin.
It shall be the object of subjecting Hisage the coated method for producing a vinyl chloride resin sheet <br/> over preparative having good productivity processability.

[0005] To this end, a conventionally used acrylic resin or the like is coated on a vinyl chloride resin sheet.
Cloth, dried and taking up using the apparatus, and it is necessary to form a target film by the crosslinked coating composition having a performance comparable to the vinylidene fluoride resin film.

[0006] sufficient pot life of as paint, it must be at least 5 hours at room temperature. As drying conditions , the temperature is 40 ° C to 200 ° C, preferably 80 ° C to 120 ° C.
You. Drying speed is slower when less than 40 ℃, 200 ℃
If the temperature exceeds the limit, thermal decomposition of the vinyl chloride resin sheet itself and volatilization of the plasticizer become remarkable. Drying time is determined by the relationship between the length of the coating speed and drying furnace, 5 seconds to 20 minutes, productivity and practical, preferably 20 seconds to 3 minutes, the solvent in the paint is less than 5 seconds Drying is insufficient, and if it exceeds 20 minutes , productivity is low.

Under the above-mentioned drying conditions, the crosslinking reaction of the paint sufficiently proceeded, and the vinyl chloride resin sheet was wound up.
Sometimes it is necessary not to cause blocking.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has the following (1) to (4).
This is the invention of (3). (1) Acrylic acid or methacrylate which is compatible with fluorine-containing copolymers (a) and (a) having a cross-linking site having active hydrogen
Based on alcohol esters of tacrylic acid having 1 to 12 carbon atoms
Brute as a main component an acrylic polymer (b), wherein the polyisocyanate compound (c) as a crosslinking agent, further, low activity at room temperature, amine organic acid salts which exhibit high activity catalysis at 40 to 200 ° C. ( A coating composition containing d) in a proportion of 0.001 to 5% by weight based on the main component. (2) Acrylic acid or methacrylate which is compatible with fluorine-containing copolymers (a) and (a) having a cross-linking site having active hydrogen
Based on alcohol esters of tacrylic acid having 1 to 12 carbon atoms
And a polyisocyanate compound (c) as a cross-linking agent, and an organic acid block of a cyclic amine or an organic acid block of a tertiary amine is added to the main component in an amount of 0.1%. A coating composition containing 001 to 5% by weight. (3) applying the coating composition of (1) or (2) above on a vinyl chloride resin sheet, drying at 40 to 200 ° C. for 5 seconds to 20 minutes, and then winding the vinyl chloride resin sheet A method for producing a coated vinyl chloride resin sheet, characterized in that:

[0009] As the vinyl chloride resin sheet in the present invention generally rigid vinyl chloride resin sheet, a soft vinyl chloride resin sheet, a vinyl resin-coated steel plates chloride, and vinyl chloride resin laminated polyester sheet is exemplified. Of these soft vinyl chloride resin sheet is used most commonly. As the vinyl chloride resin sheet in the present invention, in addition to the homopolymer of vinyl chloride, and vinyl chloride, vinyl acetate, ethylene, propylene, acrylic acid ester, at least one of the four monomers, such as methacrylic acid ester
0 wt% or less, preferably may be a copolymer with an amount of 30 wt% or less, the polymer having compatibility with respect to the homopolymer or the copolymer, such as ethylene - vinyl acetate copolymer, chloride A vinyl-vinyl acetate copolymer or the like may be blended. Further, the vinyl chloride resin sheet of the present invention is mixed with an appropriate amount of a plasticizer and is often used as a soft vinyl chloride resin sheet. As the amount of the plasticizer, per 100 parts by weight of vinyl chloride resin,
A range of about 30 to 70 parts by weight is preferably employed . The variable <br/> plasticizer, dibutyl phthalate, dioctyl phthalate, diisodecyl adipate, tricresyl phosphate, epoxidized soybean oil, epoxidized linseed oil and the like. Further, the vinyl chloride resin sheet of the present invention includes:
Conventional additives such as a lubricant, an antioxidant, an antistatic agent, a heat stabilizer, a colorant, and a flame retardant may be added.

[0010] The coating composition of the present invention is compatible with the fluorine-containing copolymer having a crosslinking site with active hydrogen (a) and (a), the number of carbon atoms of acrylic acid or methacrylic acid 1
Acrylic polymers based on 12 alcohol ester of a (b) shall be the main component.

As the fluorine-containing copolymer (a) having a crosslinking site having active hydrogen, a solvent-soluble fluorine-containing copolymer having a fluorine content of 10% by weight or more based on a fluoroolefin unit is preferably employed.

[0012] As the fluorine-containing copolymer (a), is preferably fluorine content based on fluoroolefin units 1
0-70% by weight, more preferably a 15 to 50 wt%, intrinsic viscosity measured in tetrahydrofuran at an uncured state is, it is more preferred 0.01~4.0dl / g. If the fluorine content is less than 10% by weight ,
The desired effect of improving stain resistance is reduced. Furthermore, to the extent the intrinsic viscosity is in the above enables good paintability as paint, moreover also becomes excellent physical properties of the film formed. Such fluorine-containing copolymer (a), copolymers of ethylenically unsaturated compounds as fluoroolefin and fluoroolefin copolymerizable comonomer is preferably employed.

Examples of the fluoroolefin include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene, pentafluoropropylene and the like. Of these, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride and hexafluoropropylene are particularly preferably employed. Examples of the ethylenically unsaturated compound as a monomer copolymerizable with a fluoroolefin include olefins, alkyl vinyl ethers, vinyl esters, alkyl allyl ethers, allyl esters, and acryloyl group-containing compounds. And methacryloyl group-containing compounds.

Among these, olefins, alkyl vinyl ethers, vinyl esters, and alkyl allyl ethers, which are particularly excellent in copolymerizability with fluoroolefins, are linear and have about 1 to 10 carbon atoms. Jo, branched or those having a alicyclic alkyl group is preferable.

[0015] The fluorine-containing copolymer (a), units based on the fluoroolefin that contains 30 to 70 mol% have better good <br/>. Weather resistance improving effect and is less than 30 mol% is not charged <br/> content tends to decreases the solubility to solvents exceeds 70 mol%, the risk of harm to the coating fabric work. The fluoroolefin and the ethylenically unsaturated compound of the fluorinated copolymer (a) may be used alone or in combination of two or more.

[0016] The onset facie definitive fluorocopolymer as (a), the other component, a curing agent, or to form a three-dimensional network structure by reacting between the fluorine-containing copolymer, coating solvent sex,
Since a favorable result that the acid resistance and the alkali resistance are improved is provided, those having a crosslinked site are employed.

Examples of the crosslinking site include active hydrogen-containing groups such as a hydroxyl group, a carboxyl group, an acid amide group, an amino group and a mercapto group.

Of these, a hydroxyl group is particularly preferred in that it has excellent reactivity with the polyisocyanate compound (c) used as a crosslinking agent.

[0019] introduction to such crosslinking sites of the fluorine-containing copolymer, such as hydroxyalkyl vinyl ethers, hydroxyalkyl allyl ethers, hydroxyaryl ethers, acrylic acid, a copolymer of a monomer having a crosslinking reactive sites, such as methacrylic acid allowed to process, method in which it added by reacting an acid anhydride in the fluorine-containing copolymer, and the like are employed. As a method for producing a carboxyl group or a hydroxyl group by hydrolyzing a part of the fluorinated copolymer, a fluorinated polymer obtained by copolymerizing a monomer that is a hydrolyzable ester is used. A method of generating a carboxyl group or a hydroxyl group in the fluorinated copolymer by hydrolysis is also employed. Furthermore, the hydroxyl group-containing fluorine-containing copolymer, also be employed a method of introducing a divalent carboxylic acid anhydride is reacted carboxyl groups such as succinic acid.

[0020] you compatible fluorinated copolymer (a) in the present invention, 1 to carbon atoms of acrylic acid or methacrylic acid
Acrylic polymer based on 12 alcohol esters
(B) preferably has a molecular weight of 500 to 80,000. The
Acrylic acid or methacrylic acid having 1 to 12 carbon atoms
Examples of the coal ester include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-butyl acrylate and tert-butyl acrylate. . The acrylic polymer (b) in the present invention;
Is then preferably a copolymer consisting of two or more of the above exemplified monomers, or alcohol esters of acrylic acid other than the above examples, styrene, maleic acid, vinyl esters (vinyl acetate), acrylonitrile , Methacrylonitrile, copolymers with vinylsilane and the like . If A acrylic polymer (b) has a crosslinking site,
Acrylic polymer (b) is cross-linked by reaction with the crosslinking sites of the fluorine-containing copolymer (a), coating of the coating composition becomes three-dimensional network structure, further good exhibits excellent properties
Good .

The crosslinking site of the acrylic polymer (b) is preferably a hydroxyl group. The introduction of the hydroxyl group may be carried out, for example, by using 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, or the like. 2-hydroxypropyl methacrylate,
3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate,
-Hydroxybutyl methacrylate, 3-chloro-2-
Hydroxypropyl acrylate, and monomers such as 3-chloro-2-hydroxypropyl methacrylate, said or acrylic polymer is carried out by copolymerizing a comonomer that gives a copolymer.

The acrylic polymer (b) may be a mixture of acrylic <br/> polymer having no crosslinking site and acrylic polymer having a crosslinking site. The preferred ratio of the acrylic polymer having no cross-linking site is up to 50% by weight based on the acrylic polymer having the cross-linking site.

Further,Of the present inventionPaint compositionMasterIn minutes
ToFluorine-containing copolymer(A) andAcrylic polymer
(B),A crosslinking agent is blended. This crosslinking agent contains
Phase with nitrogen copolymer (a) and acrylic polymer (b)
Melt,The main componentWhat cures is used. Heel
Polyisocyanate compound (c)
Adopted. For example, hexamethylene diisocyanate,
Non-yellowing diisocyanate such as isophorone diisocyanate
CardsandIts adduct, isocyanate group
Isocyanate blocked with a blocking agent such as
Nate and the like can be adopted as a preferable one.

[0024] In order to accelerate the cure that is cross-linked with a cross-linking agent, the catalyst but it may also be used in combination. For example, dibutyl
Tin dilaurate (DBTDL) is a fluorine-containing copolymer
It may be used in an amount of 0.001 to 2 parts by weight based on 100 parts by weight of (a) .

On the other hand, one of the amine organic acid salts (d) having low activity at room temperature, giving a sufficient pot life and exhibiting a high activity catalyst at a drying condition of 40 to 200 ° C.
At least 0.001 to 5% by weight based on the main component (fluorine-containing copolymer (a) having a cross-linking site having active hydrogen and acrylic polymer (b) compatible with (a)) Add as

As the amine organic acid salts (d),
It is selected from among temperature-sensitive amines or blocked amines generally referred to as retarding catalysts, and includes those from cyclic acid organic acid blocks such as piperazine and morpholine derivatives or tertiary amine organic acid blocks. Includes choices. In particular, a phenol salt of 1,8-diazabicyclo [5.4.0] undec-7-ene,
An octanoate, an unsaturated fatty acid salt, an organic acid block of triethylenediamine, an organic acid block of bis ( 2- dimethylaminoethyl) ether, or the like is preferably used.

The proportion of each of the main constituent components in the coating composition of the present invention is such that the content of the fluorine-containing copolymer (a) is from 30 to
It is preferable that 90% by weight and 10 to 70% by weight of the acrylic polymer (b) are used. When the amount of the fluorinated copolymer (a) is small, the fluorine content is reduced, and the intended effect of improving the weather resistance is not achieved. On the other hand, when the amount of the acryl-based polymer (b) is small, the adhesion to the substrate is low. Decrease. Fluorine-containing copolymer
(A) and the acrylic polymer (b) is within the range of the ratio of the upper Symbol their respective, without being limited to one 2
More than one species may be used in combination. The crosslinking agent is a fluorinated copolymer
It is used at a ratio of more than 0% by weight and 20% by weight or less based on the total amount of (a) and the acrylic polymer (b) .

The coating composition of the present invention contains, in addition to the main constituent components, a fluorine-containing copolymer (a) and an acrylic polymer
The total amount of (b), Ru can be further improved weather resistance by the inclusion of 0.5 to 3 wt% UV absorber. Examples of such UV absorbers include conventionally known or well-known 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-n-.
Octyloxybenzophenone, 2-hydroxy-4-
(1-methyl-2-hydroxyethoxy) benzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxypropoxy) benzophenone such as benzophenone or 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di -t- butyl phenyl) as benzotriazole, such as benzotriazole or <br/> other alone may be used in combination.

Further, an acrylic polymer (e) having a fluoroalkyl group may be added to the coating composition of the present invention to improve the water repellency of the vinyl chloride resin sheet. As the acrylic polymer (e) having such a fluoroalkyl group, when a polymer having the same cross-linking site as that of the fluorinated copolymer (a) or the acrylic polymer (b) is employed, the water repellency and the like are prolonged. Is preferable because it is held over The addition amount of the acrylic polymer (e) having such a fluoroalkyl group is about 0.1 to 30 parts by weight per 100 parts by weight of the total of the fluorine-containing copolymer (a) and the acrylic polymer (b). It is preferable to adopt in the range.

In addition, the present invention is intended to improve characteristics.
The coating composition, for example, antifoaming agent, antistatic agent, pigment,
Additives such as a dispersion stabilizer, a viscosity modifier, a leveling agent, and an anti-gelling agent may be added. Blending of the pigment,
This has the effect of hiding the coating.

The coating composition of the present invention, the such as, the fluorine-containing copolymer (a) and the acrylic polymer (b) the main constituent, a curing agent as required such as an ultraviolet absorber, fluoroalkyl acrylic polymer having a group (e), and other additives obtained by lyse the organic solvent. As the solvent used, for example toluene, aromatic hydrocarbons such as xylene, alcohols such as propanol, butanol, ethyl acetate, esters such as butyl acetate, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, an ethyl cellosolve
Various general organic solvents such as any glycol ethers and various commercially available thinners. The concentration of the coating composition components of the present invention, preferably 1 to 60 wt%,
Ri is preferably that formed by preparing a 5 to 50 wt%, preferred in workability to form a coating film.

The preparation of the coating composition of the present invention is carried out by using various equipments used for general coating, such as a ball mill, a paint shaker, a sand mill, a jet mill, a three-roll mill and a kneader.
There is no particular limitation. At this time, additives such as those described above can be added.

In the present invention, a method of forming a coating film of a coating composition on a vinyl chloride resin sheet includes vinyl chloride.
Brushing the paint composition on the resin sheet , spraying,
Etc. By applying flow coater, or applied by immersing the vinyl chloride resin sheet in the coating composition, at 40 to 200 ° C., preferably wound after drying in a range of 5 seconds to 20 minutes. For example, at 80 ° C for 30
Drying for 2 seconds is sufficient.

[0034] The thickness of the film that is formed is 2~100μm
Preferably, a sufficient effect is recognized in the thickness . The adjustment of the thickness of the coating is determined by the component concentration of the coating composition and the application conditions, but there is no problem even if a multilayer coating is formed. The shape of the vinyl chloride resin sheet is not limited at all.

[0035]

The coating composition of the present invention is characterized in that the fluorine-containing copolymer (a ) having a cross-linking site having active hydrogen has the weather resistance and durability,
And good features of the surface tension, adhesion to vinyl chloride resin sheet that by the A acrylic polymer (b), in addition to painting property by crosslinking with a polyisocyanate compound (c), a vinyl chloride resin prevent oozing of plasticizer from the sheet, also Ru provide excellent target film for preventing adhesion of dirt from the outside. To obtain a vinyl chloride resin sheet coated In practice, application of the coating composition, dry 燥後,
Wind using a winding device . It is necessary to devise a coating method to prevent blocking when the film is wound . That is, considering a single coating operation , the pot life after mixing the coating composition is required to be 8 hours or more. If it is less than 40 ° C., drying is slow, and if it exceeds 200 ° C., the vinyl chloride resin sheet is deteriorated. The drying time of 5 seconds to 20 minutes is a limitation due to the coating speed and the length of the drying oven. To achieve this, the activity at room temperature lowered, amine organic acid salts which exhibit high activity catalysis (d) acts effectively as necessary ingredients at 40 to 200 ° C..

[0036]

EXAMPLES Examples (Examples 1 to 10) and Comparative Examples (Example 11)
１４14) The coating compositions of Examples 1 to 14 having the compositions shown in Table 1 were prepared. The coating composition of Examples 1 to 14 was coated on the surface of the soft vinyl chloride resin sheet by a roll coater (Yokoyama Seisakusho, direct roll coater) so that the thickness of the coating became 15 μm.
, The temperature 100 ° C. at a coating speed of 25 m / min, that is, conditions until the drying of 100 ° C. × 30 seconds is performed is wound
Was coated cloth adjust to. After 24 hours, rewind this sheet,
It was confirmed whether or not blocking had occurred (x indicates that blocking occurred, and ○ indicates no blocking). Further, the coating composition having the same composition as that applied was placed in a 100 ml glass container, and the time (minute) at 25 ° C. at which fluidity was lost was defined as the pot life.

[0037]

[Table 1]

In Table 1, the fluorinated copolymers are as follows. FA is TFE / HBVE / n-BVE : 4
It is a copolymer copolymerized at a ratio of 8.1 / 12.5 / 39.4 (% by weight), and has an intrinsic viscosity (referred to as [η]) measured in tetrahydrofuran at 30 ° C. of 0.15 (dl /
g) . Hereinafter, FB to FF are
Only the ratio, [η], is shown. FB is CTFE / HBV
E / CHVE / EVE : 56.4 / 5.7 / 12.4 /
25.5 (% by weight) , [η] = 0.21 ( dl / g ) .
FC is HFP / HBVE / n-BVE : 66.7 /
8.0 / 25.3 (% by weight) , [η] = 0.08 ( dl
/ G ) . FD is TFE / CH ₃ COOCH = CH ₂ /
_{CH 2 = CHCH 2 OCH 2 CH} 2 OH: 53.7 / 23.
1 / 23.2 (% by weight) , [η] = 0.18 ( dl /
g ) . FE : CTFE / EVE / HBVE / Veova 9 : 39.4 / 17.2 / 9.5 / 33.9 (weight)
%) , [Η] = 0.40 ( dl / g ) . FF is TF
E / EVE / HBVE / CH ₂ = CHOCH ₂ CF ₂ CF ₂
H : 57.0 / 22.4 / 10.8 / 9.8 (weight
%) , [Η] = 0.10 ( dl / g ) . (TFE is tetrafluoroethylene, HBVE is ω-hydroxybutyl vinyl ether, n-BVE is n-butyl vinyl ether, CTFE is chlorotrifluoroethylene, CHVE
Is cyclohexyl vinyl ether, EVE is ethyl vinyl ether, HFP is hexafluoropropylene, and Veova 9 is a vinyl ester of a branched carboxylic acid (carbon number 9) (manufactured by Shell Chemical Co., Ltd.). )

The acrylic copolymers are as follows. M-1 is isobutyl methacrylate / n-butyl acrylate / 2-hydroxyethyl methacrylate: 7/2/1 copolymer obtained by copolymerizing at a ratio (molar ratio)
body. Hereinafter, M-2 to M-4 indicate only the composition ratio.
M-2 is methyl acrylate / n-butyl acrylate / glycidyl acrylate : 8/1/1. M-3 is
n-butyl methacrylate / isobutyl methacrylate / acrylonitrile / 2-hydroxyethyl methacrylate : 1/7/1/1. M-4 is methyl methacrylate / n-butyl methacrylate : 5/5.

The crosslinking agent is an isocyanate curing agent [Coronate EH (manufactured by Nippon Polyurethane)].

The catalysts are as follows. DBU,
1,8-diazabicyclo [5.4.0] undec-7-
En. Ucat-SA No. 1 is a phenol salt of DBU (manufactured by San Apro). Ucat-SA No. 10
2 is an octanoate of DBU (manufactured by San Apro). Uc
at-SA No. 103 is an oleate of DBU (manufactured by San Apro).

ToYoCAT-TF is an organic acid block of triethylenediamine (manufactured by Tosoh Corporation). ToYoCA
T-ETF is an organic acid block of bis ( 2- dimethylaminoethyl) ether (manufactured by Tosoh Corporation).

[0043]

According to the present invention, generally used without changing the apparatus and drying conditions are going to be covered process, it allows to perform a good coating treatment stain resistance to vinyl chloride resin sheet And

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C08J 7/04 CEV C08J 7/04 CEV (56) References JP-A-62-212471 (JP, A) JP-A-61-12760 (JP, A) JP-A-59-197471 (JP, A) JP-A-1-319521 (JP, A) JP-A 64-16619 (JP, A) JP-A-4-218578 (JP, A) ( 58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 175/00 B05D 7/02 B32B 27/30 C08J 7/04

Claims (3)

(57) [Claims] 1. A fluorinated copolymer (a) having a crosslinking site having active hydrogen and acrylic acid and acrylic acid compatible with (a).
Or methacrylic acid alcohol ester having 1 to 12 carbon atoms
Acrylic polymers based on Le a (b) as a main component, wherein the polyisocyanate compound (c) as a crosslinking agent, further, low activity at room temperature, amine organic acid which exhibits high activity catalysis at 40 to 200 ° C. A coating composition containing the salt (d) at a ratio of 0.001 to 5% by weight based on the main component. 2. A fluorinated copolymer (a) having a cross-linking site having active hydrogen and acrylic acid or acrylic acid compatible with (a).
Or methacrylic acid alcohol ester having 1 to 12 carbon atoms
And a polyisocyanate compound (c) as a crosslinking agent, and an organic acid block of a cyclic amine or an organic acid block of a tertiary amine. 0.001-5% by weight
Paint composition containing at a ratio of 3. The coating composition according to claim 1, which is applied on a vinyl chloride resin sheet, dried at 40 to 200 ° C. for 5 seconds to 20 minutes, and then wound up. A method for producing a coated vinyl chloride resin sheet, characterized in that: