JP3090964B2 - Thermoplastic sheet having coating composition and coating - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic sheet having the coating composition 及 beauty coating.

[0002]

Conventionally, a thermoplastic sheet with a coating, for the purpose of improving the weather resistance, are used often those protective coating with excellent coating material of relatively weather-resistant like acrylic resins.

Further, for the purpose of further improving the weather resistance, there has been proposed one coated with a protective material made of a fluororesin (Japanese Patent Laid-Open No. 60-101043).

[0004]

[It is solved by the invention Problems] Conventionally, JP thermoplastic sheet with excellent coating weatherability, known as agricultural plastic sheets 60-10104
No. 3, etc., but the adhesion between the protective coat and the sheet was poor, and it was not enough to withstand use.

[0005] Further , the coating composition used for the thermoplastic sheet having these coatings is mainly of an acrylic lacquer type, and although the workability at the time of producing the sheet is a quick-drying type, which is very good, Since it did not have a crosslinked structure, it had poor solvent resistance and stain resistance.

[0006] Further, when it is attempted to introduce a crosslinked structure by blending a curing agent to improve solvent resistance and stain resistance, a thermoplastic sheet generally has low heat resistance, and a crosslinked structure can be sufficiently obtained by heating at a low temperature. It took too much time to complete the process , causing problems such as blocking during winding .

[0007] In the case of increasing the number of cross-linking sites or adding a large amount of a reaction catalyst for the purpose of increasing the speed of cross-linking, the time required to obtain a sufficient cross-linked structure is reduced, but the pot life of the composition is extremely short. since the short to, be subjected to practical use was almost impossible.

The present invention, the conventional solve the problems of the art, i.e., excellent in good weather resistance productivity, and the thermoplastic sheet 及 beauty coating composition having excellent coating adhesion of the protective coating The purpose is to provide things.

[0009]

Means for Solving the Problems The present invention has been made to solve the above-mentioned problems, and has the following component (a):
And component (b) as the main component, component (a) and component (b)
Is 30 to 90% by weight of component (a) and component 10 is component (b).
A 70 wt%, the total of components (a) and component (b)
A mixture of an organic acid and an amine per 100 parts by weight
Or 0 . And characterized in that it contains 05 to 2 parts by weight
Coating composition, and the thermoplastic resin sheet, to provide a thermoplastic sheet having a coating film formed by the coating composition. (A) A fluorine-containing copolymer having a hydroxyl group. (B) C1-C12 alcohol and acrylic acid or
With a polymerized unit of ester with tacrylic acid as an essential component,
Having a molecular weight of 500 to 80,000 and a phase with component (a)
Acrylic polymer that dissolves.

Examples of the thermoplastic resin as the base material of the thermoplastic sheet having the coating of the present invention include a vinyl chloride resin, a polyethylene resin, and a polyester resin.
Among them, a vinyl chloride resin, particularly a soft vinyl chloride resin, is most generally used. Examples of the vinyl chloride resin include, besides a homopolymer of vinyl chloride, at least one of monomers such as vinyl chloride and vinyl acetate, ethylene, propylene, acrylate, and methacrylate.
Seeds 40 wt% or less, preferably may be a copolymer with an amount of 30 wt% or less, the polymer is these homopolymers or with compatibility with the copolymer, such as ethylene -
A blend of a vinyl acetate copolymer, a vinyl chloride-vinyl acetate copolymer, or the like may be used. Also,
An appropriate amount of a plasticizer is blended with the vinyl chloride resin, and is often used as a soft vinyl chloride resin. The amount of the plasticizer is 3 parts per 100 parts by weight of the vinyl chloride resin.
A range of about 0 to 70 parts by weight is preferably employed. Also,
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, diisodecyl adipate, tricresyl phosphate, epoxidized soybean oil, and epoxidized linseed oil. Further, ordinary additives such as a lubricant, an antioxidant, an antistatic agent, a heat stabilizer, a colorant, and a flame retardant may be added to the vinyl chloride resin.

Further, a surfactant may be added to the vinyl chloride resin for the purpose of preventing fogging. As such a surfactant, a nonionic surfactant is preferably employed.

In the present invention, the coating composition for forming a film on the thermoplastic resin sheet includes the above-mentioned (a)
It shall be the chief components and component (b). Here, (a) formed
As the component, a solvent-soluble fluorinated copolymer having a fluorine content of 10% by weight or more based on a fluoroolefin unit is preferably employed.

The component (a) has a fluorine content of 10% by weight or more, preferably 10 to 70% by weight, more preferably 15 to 50% by weight based on the fluoroolefin unit, and is in an uncured state. Those having an intrinsic viscosity of 0.01 to 4.0 dl / g measured in tetrahydrofuran are used. If the fluorine content is less than 10% by weight, the intended effect of improving weather resistance is reduced. When the intrinsic viscosity is in the above range, the coatability of the coating composition is good, and the physical properties of the formed film are also excellent. Such fluorine-containing copolymer, a copolymer of fluoroolefin 及 beauty said fluoroolefin copolymerizable comonomer can be mentioned. As the comonomer,
Ethylenically unsaturated compounds other than fluoroolefins are 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 include olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, acryloyl group-containing compounds, methacryloyl group-containing compounds, and the like.

[0015] Of these, olefins having excellent copolymerizability with fluoroolefins, vinyl ethers, vinyl esters, an allyl ethers number 10 about a straight, branched or cycloaliphatic Those having a cyclic alkyl group are preferred. (A) in component units based on the fluoroolefin is preferably to contain 30 to 70 mol%, the weather resistance improving effect and is less than 30 mol% is not sufficient, dissolving 70 mol% for is exceeded and a solvent Properties tend to decrease, which may hinder the coating operation as a coating composition. Further, the fluorine-containing copolymer, fluoroolefin 及 beauty ethylenically unsaturated compound may each be a single, or may be two or more kinds are used in combination.

Component (a) in the coating composition of the present invention
The hydroxyl group of the component (A) is a component, a curing agent, and a component (a)
And between the molecules and the reaction, three-dimensional network structure is formed, solvent resistance of the film, acid resistance, alkali resistance is improved.

The hydroxyl groups are usually Ru excellent reactivity etc. isocyanate curing agent to be used as the curing agent.

The introducing methods to such the hydroxyl group of the fluorine-containing copolymer, such as hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether and copolymerizing a monomer having a hydroxyaryl <br/> Biniruete Le of which hydroxyl <br / > such as caulking Ru way is adopted. Further, as a method in which a partially exploded of the fluorinated copolymer after by copolymerizing a monomer having a hydrolyzable ester group, a hydroxyl in the copolymer by hydrolyzing the copolymer A method for generating a group is also employed.

The principal component a is pre Symbol coating composition of the present invention
(A) to component and compatible component (b), the alcohol ester of 1 to 12 carbon atoms of acrylic acid or methacrylic acid heavy
An acrylic polymer having a combined unit as an essential component and a molecular weight of 500 to 80,000. Such alcohol esters include methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-
Butyl methacrylate, n- butyl acrylate 及 beauty t
tert-butyl acrylate and the like are exemplified. Also,
Preferably, the copolymer consisting of two or more of these monomers, or alcohol esters of acrylic acid or methacrylic acid other than the above examples, styrene, maleic acid, vinyl esters (vinyl acetate), acrylonitrile,
Copolymers with methacrylonitrile, vinylsilane and the like are used. In particular, an acrylic polymer having a cross-linking site
But cross-linked by reaction with the hydroxyl groups of component (a), coating the coating composition becomes three-dimensional network structure, exhibits excellent characteristics preferable.

[0020] In the component (b), as the crosslinking site, a hydroxyl group, a glycidyl group, an amide group, such as silanol groups Ru preferred der. For example, the introduction of a hydroxyl group is performed by using 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
-Hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate,
4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate and the like, and glycidyl groups introduced by glycidyl acrylate, glycidyl methacrylate, (β
For example, acrylamide, methacrylamide, dimethylacrylamide, dimethylmethacrylamide, N-tert-butylacrylamide, N-tert-butylmethacrylamide, N-tert-butylmethacrylamide, and the like. octyl acrylamide, N- octyl methacrylamide, diacetone acrylamide, and diacetone methacrylamide, also the introduction of silanol groups and a monomer with the acrylic polymer given <br/> obtain monomers such as vinyl silane It is carried out by copolymerization.

Further, silanol group, isocyanate silane or a hydroxyl group-containing acrylic polymer can be introduced by a method of adding a silane coupling agent.

Here, the component (b) has a crosslinking site.
It may be a mixture of an acrylic polymer and an acrylic polymer having no crosslinking site. The latter amount is preferably Ru is 50 wt% or less with respect to the former.

Furthermore, it a curing agent to a principal component of the coating composition (a) component及 beauty component (b).
As the curing agent, compatible with component (a) 及 beauty component (b),
What cures them is used. As such a curing agent, polyisocyanates, for example, non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and adducts thereof, and blocked isocyanates in which isocyanate groups are blocked with a blocking agent such as phenol are preferably used. I can do it. Also, metallic alkoxide, polybasic acid, epoxy, silanol-based curing agents can be used. Special
, The polyisocyanate-based, metal alkoxide is preferred. Or hunt curing agent is very useful in the formation of three-dimensional network structure of the acrylic polymer having a fluorine-containing copolymer and a crosslinking site having a hydroxyl group.

[0024] for the purpose of accelerating the curing with a curing agent, the catalyst but it may also be used in combination. Such catalysts, such as dibutyltin the isocyanate curing agent Suzuji laurate (DBTDL) is, with respect to component (a) 100 parts by weight 0.
It is used in a ratio of 001 to 2 parts by weight.

The principal component der in the coating composition of the present invention
The proportions of the components (a) and (b) are
Components 30 to 90 wt%, 10 to 70 wt% (b) component. When the component (a) is small, the fluorine content decreases,
Improvement of weather resistance for the purpose can not be achieved, whereas,
When the amount of the component (b) is small, the adhesiveness to the substrate is reduced.
(A) the component及 beauty component (b) respectively may be used in combination of two or more without being limited to one in the range of proportions described above. The curing agent is a total of 10 components (a) and (b).
It is used in a ratio of 0 to 20 parts by weight with respect to 0 parts by weight.

The coating composition of the present invention further comprises:
Containing mixture or neutralize was a combination of organic acids and amines.

[0027] In the organic acids, the carboxyl group or Ri is preferably der those having a sulfo group, sulfonic acids such as p-toluenesulfonic acid, p-hydroxybenzoic acid, and benzoic acids such as benzoic acid may be mentioned . These are C
at-6000, Cat-5000, Cat-4040
(Both are Mitsui Toatsu) and are marketed under such trade names. The organic acids may be used alone or as a mixture of two or more.

[0028] In the amines, primary, secondary, none of the amines of the tertiary available, specifically, triethylamine, trimethylamine, triethanolamine, triethanolamine, diethylenetriamine, triethylenediamine, triethylenetetramine And the like.

[0029] Organic acids and amines are optimized paintability 及 beauty curable by combined use is effective by antiblock. As such a combined method , a mixture of an organic acid and an amine may be added at the time of preparing the coating composition, or a neutralized product of the organic acid and the amine may be added.
A neutralized product of an organic acid and an amine is commercially available as Cat-6003B (Mitsui Toatsu).

Mixtures of these organic acids and amines in combination
Or amount of the neutralized product is, (a) component and (b) total 100 parts by weight of those than zero components. It is 0.5 to 2 parts by weight . This range
Is added , the blocking resistance and the physical properties of the coated thermoplastic sheet are excellent .

[0031] the coating composition, in addition to the above KiNaru min,
Component (a)及 Beauty (b) the total amount of the components to 0.5 to 20
Ru can further improve the weather resistance by the inclusion of weight percent of UV absorber. As such an ultraviolet absorber, conventionally known or well-known 2-hydroxybenzophenone, 2,2
4-dihydroxybenzophenone, 2-hydroxy-4
-N- Ok Chiruo carboxymethyl benzophenone, 2-hydroxy-4- (1-methyl-2-hydroxyethyl) ethoxy benzophenone, 2-hydroxy-4- (2-hydroxy-3
Benzophenones such as-(methacryloxy) propoxybenzophenone and 2- (2'-hydroxy-5 '
-Methylphenyl) benzotriazole, 2- (2'-
Hydroxy -3'5'- di -t- butyl phenyl) as benzotriazole, such as benzotriazole or used in combination alone.

Further, an acrylic polymer (c) having a fluoroalkyl group may be added to the coating composition to improve the water repellency of the plastic sheet . (C) As the component, the same water before SL component (a)
Acid, or by adopting a material having a similar cross-linking site and component (b) in the case of having a crosslinking site is preferable because such water repellency is maintained for a long time. The amount of component (c) <br/>, it is preferable to employ a range of total 0.1 to 30 parts by weight per 100 parts by weight of component (a) 及 beauty component (b).

In addition, for the purpose of improving the properties, the coating composition may contain additives such as an antifoaming agent, an antistatic agent, a pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, and an anti-gelling agent. It can also be blended. The incorporation of the pigment has the effect of shading the coating.

The coating composition of the present invention is as described above ,
Component (a) and (b) principal component, such as component, a curing agent as necessary, ultraviolet absorbers, obtained by lyse the organic solvent component (c), other additives. As the solvent used, for example toluene, aromatic hydrocarbons such as xylene, propanol and alcohols such as butanol, ethyl acetate, esters such as butyl acetate, methyl ethyl ketone, ketones such as methyl isobutyl ketone, such as ethyl cellosolve glycol ethers, such as more commercial thinners, Ru include various general organic solvents. The concentration of the film forming component is 1 to
It is preferable that the composition is adjusted to 60% by weight, preferably 5 to 50% by weight in terms of workability of forming a coating.

[0035] Made tone of the coating composition, such as a ball mill, a paint shaker, a sand mill, a jet mill,
It is carried out by using various devices used for ordinary coating, such as a three-roll mill and a kneader, and is not particularly limited. At this time, additives such as those described above can be added.

[0036] In the present invention, a method of forming a coating film of the coating composition to the thermoplastic resin sheet, brush coating a coating composition for thermoplastic resin sheet, spray spray is applied such as by flow coating, or in the coating composition is applied by immersing the thermoplastic resin sheet, the solvent performs a sufficient drying to volatilize and then heating or a coating film allowed to stand at room temperature. Pressurized heat at this time, the temperature below which no deformation of the thermoplastic resin sheet, is sufficient under the conditions of example 60 ° C. for 10 minutes.

A sufficient effect is recognized when the thickness of the formed film is 2 to 100 μm. Adjustment of the thickness of the coating is determined by the component concentration and coating condition of the coating composition, there is no problem even if coated is formed on the multilayer. The shape of the thermoplastic resin sheet is not limited at all.

[0038]

EXAMPLES [Examples 1 to 9, Comparative Examples 1 to 4] Coating compositions (paints) No. 1 to 1 having the compositions shown in Table 1
13 was prepared. Paint Nos. 1 to 13 were applied to the surface of the soft vinyl chloride resin sheet by adjusting the thickness of the coating formed by the gravure coater to 15 μm.
A cured film was formed by heating at 200C for 20 seconds.

Table 2 shows the results of the following evaluation tests performed on the sheet on which the coating was formed. Contact angle: the contact angle of water was measured 及 beauty n- hexadecane. Adhesion: The adhesion of the coating was measured according to the method of ASTM-3359 initially, after immersion in warm water (60 ° C. × 30 days), and after treatment with a sunshine weather meter for 1000 hours, and evaluated by the number of squares remaining. Weather resistance: Color measurement device (SM-SM- manufactured by Suga Test Instruments Co., Ltd.)
3), and the yellowing deterioration is measured by the difference (ΔY.
I). Blocking resistance: 80 ° C. after heat curing at 80 ° C. for 20 seconds
When lamination was carried out at a load of 1 kg / cm ² for 24 hours, な し was given without blocking, X was given with blocking, and Δ was given with slight blocking. Pot life: After standing at room temperature for 4 hours, no gelation was evaluated as ○, and gelation was evaluated as x.

[0040]

[Table 1]

In Table 1, the fluorinated copolymers are as follows. FA is TFE / HBVE / n-BVE = 48.1 /
12.5 / 39.4 (wt%) copolymer having an intrinsic viscosity (referred to as [η]) of 0.15 dl / g measured in tetrahydrofuran at 30 ° C. (same as below). FB is CTFE / HBVE / CHVE / EVE = 5
6.4 / 5.7 / 12.4 / 25.5, [η] = 0.2
1 dl / g. FC is HFP / HBVE / n-BVE = 66.7 /
8.0 / 25.3, [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, [η] = 0.18 dl / g. FE is CTFE / EVE / HBVE / Vova 9 = 3
9.4 / 17.2 / 9.5 / 33.9, [η] = 0.4
0 dl / g. FF is TFE / EVE / HBVE / CH ₂ ＣＨCHO
_{CH 2 CF 2 CF 2 H =} 57.0 / 22.4 / 10.8
/9.8, [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; )

The acrylic copolymers are as follows. M-1 is isobutyl methacrylate / n-butyl acrylate / 2-hydroxyethyl methacrylate = 7 /
A copolymer copolymerized at a ratio of 2/1 (molar ratio) (the same applies hereinafter). 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 fluoroalkyl group-containing acrylic polymer has a content of CH ₂ ＣＨCHCOOCH ₂ CH ₂ (CF ₂ ) ₁₀ F / isobutyl methacrylate / n-butyl acrylate / 2-hydroxyethyl methacrylate = 20/60/10/10% by weight. Polymer.

The curing agent is an isocyanate curing agent [Coronate EH (manufactured by Nippon Polyurethane)]. Ultraviolet absorber, (manufactured by joint Yakuhin) Biosorb 130. The solvent is xylene.

The numbers in Table 1 are parts by weight (DB
The TDL number is ppm based on the total amount of the polymer.

[0046]

[Table 2]

Example 10 The procedure of Example 1 was repeated, except that the drying conditions were changed to 120 ° C. for 1 minute, and the same effects as in Example 1 were obtained.

[0048]

The thermoplastic sheet having the coating of the present invention is extremely excellent in weather resistance because the coating of the specific coating composition is formed while maintaining good adhesion. Blocking hardly occurs, and industrial production is easy.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08J 7/04 C08J 7/04 C08K 3/24 C08K 3/24 5/09 5/09 5/17 5/17 C08L 27/12 C08L 27 / 12 33/06 33/06 C09D 133/06 C09D 133/06 (56) References JP-A-64-9274 (JP, A) JP-A-62-212471 (JP, A) JP-A-62-192470 (JP, A) JP-A-59-197471 (JP, A) JP-A-1-247473 (JP, A) JP-A-1-1588082 (JP, A) JP-A-2-248476 (JP, A) 2-189377 (JP, A) JP-A-2-150404 (JP, A) JP-A-2-53872 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 127/12 C09D 133/06 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1)The following components (a) and (b) are the main components
And the ratio of the component (a) to the component (b) is 30 to 30%.
90% by weight, 10 to 70% by weight of the component (b),
(A)componentAnd (b)componentOrganic per 100 parts by weight of
acidWhenAminesA mixture ofNeutralized materialIs 0.05
~ 2Parts by weightCharacterized byCoating composition.
(A) A fluorine-containing copolymer having a hydroxyl group. (B) carbon number
1 to 12 alcohols and acrylic acid or methacrylic acid
Having a polymerization unit of an ester as an essential component, having a molecular weight of 50
0 to 80,000, which is compatible with the component (a)
Polymer. 2. A thermoplastic sheet having a coating formed by the coating composition according to claim 1 on a thermoplastic resin sheet.