JP2841454B2 - Plastic laminate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a plastic laminate excellent in surface hardness, scratch resistance, abrasion resistance, flexibility, and non-glare properties.

[Prior Art] Conventionally, as a method for imparting abrasion resistance and non-glare property to a plastic surface, a method of applying a radiation-curable layer in which a fine powder such as silica or titanium oxide is blended as a matting agent with a radiation-curable composition. Are known (for example, Japanese Unexamined Patent Publication No.
58036).

[Problems to be Solved by the Invention] However, the above-mentioned conventional plastic laminate has the following problems. Paints in which a matting agent is simply mixed and dispersed in a radiation-curable composition have poor dispersion stability of the matting agent,
The dispersed particles undergo secondary aggregation over time, causing hard sedimentation that is difficult to redisperse, and it is difficult to form a uniform cured film having non-glare properties.

Further, there is a problem that particles protrude from the surface of the cured film and the wear resistance is reduced. In addition, the degree of matting is unstable and has a non-glare property, but has a serious problem such as an increase in haze.

An object of the present invention is to solve the above problems and to provide a plastic laminate excellent in surface hardness, scratch resistance, flexibility and non-glare properties.

Means for Solving the Problems In order to achieve the above object, the present invention provides the following constitutions: 1 a flexible plastic layer (I) and a radiation-cured layer (I
I) is a plastic laminate obtained by laminating in this order, wherein said radiation-cured layer (II) comprises at least one monomer (A) having three or more (meth) acryloyloxy groups in one molecule. A radiation curable monomer comprising at least one kind of a monomer (B) having one or two ethylenically unsaturated double bonds in one molecule, and an organic material in which a dispersion stabilizing resin is previously dissolved. A plastic laminate, which is a cured layer of a radiation-curable composition comprising: a silica particle dispersion having an average particle diameter of 0.5 to 2.5 μm dispersed and pulverized in a solvent.

2. The plastic laminate according to the preceding item, wherein the ratio of the monomers in the composition is 20 to 90% by weight of the monomer (A) and 10 to 80% by weight of the monomer (B).

3 The amount of the silica particles in the composition is 100
The plastic laminate according to claim 1, wherein the amount is 3 to 25 parts by weight with respect to part by weight.

As the organic polymer film constituting the flexible plastic layer used in the present invention, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6
-Films composed of polyester polymers such as naphthalene dicarboxylate, polycarbonates, acrylate copolymers or methacrylate copolymers, but are not limited thereto.

These polymer films can be used as they are in an unstretched state, but stretched ones are preferred because the properties are improved. For example, a uniaxially stretched one is preferably provided with optical anisotropy, and a biaxially stretched one is improved in mechanical properties, thermal properties and dimensional stability.

Among these organic polymer films, a film made of polyethylene terephthalate is preferred from the viewpoints of optical and strength and that a film having excellent uniformity is easily obtained.

As polyethylene terephthalate used in the present invention, homopolyethylene terephthalate (generally, heat of fusion of crystal of about 10 cal / g) is generally used, but heat of fusion of crystal is 8ca.
If it is l / g or more, for example, it may include a copolymerized polyethylene terephthalate in which about 5% of another polyester-forming component is copolymerized or a polyester blend in which about 5% of another polyester is blended. .

The film made of polyethylene terephthalate used in the present invention includes an acrylic resin, polyester resin, polyurethane dissolved or emulsified or suspended in water and / or an organic solvent in order to improve the adhesion between the cured layer and polyethylene terephthalate. Those coated with a resin or the like are preferred. In particular, those obtained by undercoating a reaction product of a vinyl copolymer containing a hydroxyl group and a partial ester group of phosphoric acid with a polyisocyanate compound (described in JP-B-58-35145), or an acrylic compound on a hydrophilic group-containing polyester resin The undercoating of the composition comprising the grafted copolymer and the cross-linking agent improves the adhesion between the cured layer and the polyethylene terephthalate film,
It is preferable as a film having excellent durability such as boiling water resistance.

In the present invention, three or more (meth) acryloyloxy groups in one molecule (here, the (meth) acryloyloxy group is an abbreviation of an acryloyloxy group and a methacryloyloxy group). In the following description, the term “△△△ (meta) □□□” is abbreviation of “△△△ □□□” and “△△△ meta □□□”. As A), 3 per molecule
Examples of the polyhydric alcohol having at least three alcoholic hydroxyl groups include compounds in which three or more hydroxyl groups are esterified (meth) acrylic acids.

Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples thereof include dipentaerythritol hexa (meth) acrylate and trimethylolpropane tri (meth) acrylate.

These monomers (A) may be used alone or in combination of two or more.

The proportion of these monomers (A) used is preferably 20 to 90% by weight, more preferably 30 to 80% by weight, based on the total amount of the polymerizable monomers.

When the amount of the monomer (A) is less than 20% by weight, a cured film having a sufficient abrasion resistance cannot be obtained.
If the amount is more than the weight percentage, the shrinkage due to polymerization is large, and the cured film is undesirably distorted or the flexibility of the film is reduced.

As the monomer (B) having one or two ethylenically unsaturated double bonds in one molecule in the present invention, any ordinary monomer having radical polymerization activity can be used.

Examples of the compound having two ethylenically unsaturated double bonds in the molecule include the following (meth) acrylates (a) to (f).

(A) (meth) of alkylene glycol having 2 to 12 carbon atoms
Acrylic acid diesters: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( (B) (meth) acrylate diesters of polyoxyalkylene glycols: diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol diester (Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc. (c) (meth) acrylic acid diesters of polyhydric alcohols: pentae (D) Bisphenol A or (meth) acrylic acid diesters of bisphenol A hydride ethylene oxide and propylene oxide adducts: 2,2-bis (4-acryloxyethoxyphenyl) propane, 2, 2'-bis (4-acryloxypropoxyphenyl) propane and the like (e) A terminal isocyanate group-containing compound obtained by previously reacting a diisocyanate compound with two or more alcoholic hydroxyl group-containing compounds, Urethane (meth) acrylates having two or more (meth) acryloyloxy groups in the molecule obtained by reacting acrylate: (f) acrylic acid or methacrylic compound in the compound having two or more epoxy groups in the molecule Obtained by reacting acid Epoxy having two or more (meth) acryloyloxy group in the molecule (meth) acrylates: and the like.

Compounds having one ethylenically unsaturated double bond in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n- and i-propyl (meth) acrylate, n-, sec- and t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, polyethylene glycol mono (Meth) acrylate, polypropylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-hydroxyethyl (meth) acrylamide,
N-vinylpyrrolidone, N-vinyl-3-methylpyrrolidone, N-vinyl-5-methylpyrrolidone and the like can be mentioned.

These monomers (B) may be used alone or in combination of two or more.

The use ratio of these monomers (B) is preferably from 10 to 80% by weight, more preferably from 20 to 70% by weight, based on the total amount of the monomers.

If the amount of the monomer (B) exceeds 80% by weight, it is difficult to obtain a crosslinked cured film having sufficient abrasion resistance, which is not preferable. If the amount is less than 10% by weight,
It is not preferable because the flexibility of the film is reduced and the adhesion to the substrate is reduced.

The silica particles blended in the radiation curable composition of the present invention are preferably fine powders of silicon dioxide. Silica particles, which are dispersed in an organic solvent in which a dispersion stabilizing resin is dissolved in advance and then dispersed and pulverized using a wet disperser, etc., have the effect of improving the sedimentation of the particles in the paint and the light transmittance of the coating film. It is preferred in terms of. Sand mills, ball mills, sand grinders, etc.
And an impeller mill. Among these dispersers, a sand grinder is preferable because it can continuously disperse fine particles and has a high dispersion speed.

The average particle size of the dispersion-milled silica fine particles is 0.5 to
It is 2.5 μm, preferably 0.7 to 2.0 μm. If the average particle diameter is less than 0.5 μm, sufficient non-glare properties cannot be obtained,
If it exceeds 2.5 μm, the sedimentation of the particles in the paint is large, which is not preferable.

The dispersion-stabilizing resin used in the present invention suppresses the re-aggregation and finally sedimentation of the pulverized particles by dissolving the silica particles in an organic solvent in advance when the silica particles are dispersed and pulverized in the solvent. The organic resin is added in a small amount for the purpose of carrying out the process, and this resin is adsorbed on the surface of the silica particles that have been subjected to the dispersion and pulverization treatment, thereby controlling the affinity of the particle surface and imparting dispersion stability. Examples of the resin include an interaction group that is well adsorbed on the surface of the inorganic silica, such as an alcoholic hydroxyl group and a carboxyl group, and an interaction group having an affinity for an organic solvent, such as an alkyl group.
A resin having an allyl group, an ester group, a butyral group and the like in the molecule is preferably used. Specifically, butyral resin, acrylic copolymer resin, cellulose derivative, polyester resin ("Byron", manufactured by Toyobo Co., Ltd.)
And the like.

Among these dispersion stabilizing resins, butyral resin is particularly preferably used because of its good compatibility with the radiation-curable monomer and good interaction with silica particles.

As the butyral resin, polyvinyl butyral may be mentioned. The polyvinyl butyral may be any resin that is generally commercially available and soluble in an organic solvent, and is preferably a resin having a high degree of butyralization and a relatively low average molecular weight used for coating. Those with a degree of butyralization of about 63 mol% and an average degree of polymerization of 250 to 300 have excellent solubility in solvents,
It is particularly preferred because of its low viscosity.

The amount of the dispersion stabilizing resin is preferably 1.0 to 100 parts by weight, more preferably 3 to 50 parts by weight, per 100 parts by weight of the silica particles.
Parts by weight. If the dispersion stabilizing resin is less than 1.0 part by weight,
If the sedimentation of the particles in the paint is large, and if it exceeds 100 parts by weight, a cured film having sufficient abrasion resistance cannot be obtained.

The dispersion stabilizing resin is dissolved in an organic solvent before dispersing the silica particles in the organic solvent. By mixing the silica particles before the dispersion and pulverization treatment, the secondary aggregation and sedimentation of the particles in the paint are suppressed.

The following are examples of the organic solvent that dissolves the dispersion stabilizing resin.

Methanol, ethanol, isopropyl alcohol,
Alcohols such as n-butanol and ketones such as acetone and methyl ethyl ketone.

Acetates such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene;

Silica fine particles that have been subjected to predetermined dispersion pulverization alone can sufficiently exhibit the non-glare property, which is one object of the present invention, but are further dispersed and pulverized for the purpose of adjusting the unevenness and non-glare property of the non-glare film surface. Second untreated silica particles can be added. Normal,
The average particle size of the second silica particles is 2.5 to 15 μm, preferably 3.5 to 10 μm, which is larger than the first silica particles.
Is used. If the average particle diameter is less than 2.5 μm, the unevenness of the non-glare surface is not changed, and if the average particle size exceeds 15 μm, the unevenness of the non-glare surface becomes too large, and the particles that have come out of the surface are cut off, resulting in reduced wear resistance. Is not preferred.

The properties of the particles may be either hydrophilic or hydrophobic, but hydrophobic silica obtained by treating the particle surface with an inorganic or organic substance is preferably used because aggregation in the paint is less likely to occur.

When the second silica is used alone, because of its large particle size, sedimentation starts promptly after dispersion, which causes remarkable hindrance to the subsequent steps such as coating the composition. When added to the composition, sedimentation continues to be substantially suppressed for a time that does not interfere with subsequent steps.

The preferred blending amount of the silica particles in the radiation-curable composition is 3 to 25 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the radiation-curable composition. If the silica particles are less than 3 parts by weight, sufficient non-glare properties cannot be obtained, and if it exceeds 25 parts by weight, irregularities on the non-glare surface become irregular, haze is remarkably increased, transparency is lowered, and cloudiness is caused. Absent.

One method for curing the radiation-curable composition of the present invention is to irradiate ultraviolet rays. In this case, it is desirable to add a photopolymerization initiator to the composition. Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone,
Benzophenone, 2-chlorobenzophenone, 4,4'-
Dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methylbenzoylformate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone 2,2-dimethoxy-2-phenylacetophenone,
Carbonyl compounds such as 1-hydroxycyclohexylphenyl ketone, sulfur compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone and 2-methylthioxanthone, benzoyl peroxide, di-t-butyl peroxide and the like And the like. These photopolymerization initiators may be used alone or in combination of two or more. The use amount of the photopolymerization initiator is suitably 0.01 to 10 parts by weight based on 100 parts by weight of the polymerizable monomer composition. When electron beam or gamma ray is used as the curing means, it is not always necessary to add a polymerization initiator.

The radiation-curable composition used in the present invention has a known thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, 2,5-t-butylhydroquinone, and the like to prevent thermal polymerization during production and dark reaction during storage. It is desirable to add an agent. The amount added is based on the total weight of the polymerizable compound.
0.005 to 0.05% by weight is preferred.

The radiation-curable composition used in the present invention can be mixed with an organic solvent within the range not impairing the object of the present invention, for the purpose of improving workability during coating and controlling the coating film thickness. .

As the organic solvent, those having a boiling point of about 50 ° C. to 150 ° C. are easy to use from the viewpoint of workability during coating and dryness before and after curing. Specific examples include methanol, ethanol,
Examples thereof include alcohol solvents such as isopropyl alcohol, acetate solvents such as methyl acetate and ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, aromatic solvents such as toluene, and cyclic ether solvents such as dioxane. These solvents may be used alone or as a mixture of two or more.

Various additives can be added to the radiation-curable composition used in the present invention, if necessary, as long as the object of the present invention is not impaired. For example, antioxidants, light stabilizers,
Examples include stabilizers such as ultraviolet absorbers, surfactants, leveling agents, and antistatic agents.

[Production Method] The plastic laminate of the present invention is produced by applying and curing the radiation-curable layer (II) on the flexible plastic layer (I).

As a means for applying the radiation-curable composition of the present invention, commonly used application methods such as brush coating, dip coating, knife coating, roll coating, spray coating, flow coating, and spin coating (spinner, wooler, etc.) are used. It is easily applicable. Each method has its own characteristics, and the coating method is appropriately selected depending on the required performance of the laminate or the intended use.

Examples of a method for curing the radiation-curable composition of the present invention include a method of irradiating an active energy ray such as an ultraviolet ray, an electron beam, or a gamma ray. Practically, the method using ultraviolet irradiation is simple and preferable. Examples of the ultraviolet light source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and a carbon arc lamp.

The excellent effect of the present invention is that a composition comprising a radiation-curable layer (II), a radiation-curable monomer mixture, a dispersion-stabilizing resin, and dispersion-milled specific silica particles is blended on a plastic layer (I). It is caused by using.

The silica particles that have been subjected to the dispersion and pulverization treatment have a property that the particles are appropriately dispersed in the cured film and exhibit non-glare properties. When a specific silica is blended as in the present invention, a cured film having excellent anti-glare properties and excellent wear resistance can be obtained. However, silica particles alone have poor stability in the particles in the coating. As a result of blending the silica particles and the dispersion stabilizing resin with the monomer mixture as in the present invention, a remarkable effect that the dispersion stability of the silica particles is excellent, the non-glare property is uniform, and the abrasion resistance of the coating film is excellent. Is generated.

Regarding the paint stability, for example, there is some kind of bond between the hydroxyl group of the butyral resin and the terminal silanol group of the silica, and a protective film of the butyral resin is formed on the silica surface, which inhibits the aggregation of the particles, and furthermore, the organic paint. It is presumed that the affinity was improved and sedimentation of the silica particles in the paint was suppressed.

The laminate of the present invention has excellent surface hardness, excellent wear resistance, and good non-glare properties, and thus can be applied to a wide range of applications. For example, it can be advantageously used in fields where mattness is required, such as filters for CRTs, membrane switches, displays, nameplates, and covers for calculators and instruments.

[Characteristic Testing Method / Evaluation Criteria] The property measuring method and evaluation criterion in the present invention are as follows.

Abrasion resistance The surface of the hardened layer is rubbed with steel wool # 0000, and the hardness of the hardened layer is examined.

 The judgment was made as follows.

 S3: Hardly scratched even with strong friction.

 S2: If you rub very strongly, you will get a little scratch.

 S1: Scratch even with weak friction.

Polyethylene terephthalate without any abrasion-resistant coating layer has rank S1.

Adhesiveness Cross cut (1mm ² square 100
), And Nichiban cellophane tape (24mm)
Width) was attached, and the peeling area after abrupt peeling at a peeling angle of 180 ° was ranked as follows.

Adhesion index A5: Peeling area 10% or less A4: 〃20% or less A3: 〃30% or less A2: 〃40% or less A1: 越 え る Exceeding 40% Flexible 1 cm width and 5 cm length from laminate Was cut out and wound around a stainless steel rod with the hardened layer facing out, and the minimum diameter where cracks did not occur was examined.

After the laminate was immersed in boiling water for 1 hour, appearance abnormality such as generation of cracks was observed, and the same adhesion test was performed.

Humidity and heat resistance After performing a moist heat test at 60 ° C and 90% RH using a constant temperature and humidity layer (Tavaispec Co., Ltd. Platinous Humider PH-1G type), observe appearance changes such as cracks,
Further, an adhesion test with the above-mentioned abrasion resistance test was similarly performed.

Haze value (haze) Measured according to JIS K-6714 using an integrating sphere type light transmission device (HTR meter SEP-H-2, Nippon Seimitsu Optical Co., Ltd.).

Surface glossiness The surface glossiness at an incident angle of 60 ° was measured according to JIS Z-8741 using a glossiness measuring device (Suga Test Instruments Co., Ltd., digital variable-angle gloss system UGV-4D).

Dispersion stability 10 g of the coating material was collected in a 20-ml stoppered test tube, and the particles were allowed to stand at room temperature for 24 hours.

 ：: No sedimentation of particles.

Δ: Particles settled in about half, and a transparent layer was formed in the upper part and a particle-containing layer was formed in the lower part.

 ×: Particles settled at the bottom, and most of them were transparent layers.

Example 1 Example 1 After uniformly dissolving 1.0 part by weight of a butyral resin (S-LEC BL-1 manufactured by Sekisui Chemical) in 100 parts by weight of n-butanol, silica powder (“Syloid” 150 average particle diameter 2.5 μm manufactured by Fuji Devison Chemical Co., Ltd.) ) Was added and uniformly dispersed to obtain a solution. Using a sand grinder (SLG-1 / 2G, manufactured by Igarashi Kikai Seisakusho), the silica dispersion was discharged onto a glass medium of 1 to 1.5φ at a discharge rate of 200 ml / min and a rotation speed of 1600 rpm for 1 pas.
The process was performed to obtain an alcohol dispersion of silica that had been subjected to dispersion and pulverization. The average particle diameter of the silica particles in the obtained dispersion is 1.4 μm by particle size distribution measurement using an image analyzer.
m.

Examples 2 to 5, Comparative Example 1 A biaxially stretched polyethylene terephthalate film ("Lumirror" manufactured by Toray Industries, Inc.) having a thickness of 100 μm was coated on one surface with 70 parts by weight of dipentaerythritol hexaacrylate and 30 parts by weight of N-vinylpyrrolidone. Using a bar coater, a composition obtained by stirring and mixing the silica dispersion obtained in Example 1 with the silica particles and the butyral resin in the amounts shown in Table 1, toluene 40 parts by weight, and 1-hydroxycyclohexyl phenyl ketone 5 parts by weight was used. It was applied to a thickness of 3 μm. This was left for 30 seconds in a hot air dryer at 80 ° C, and after the solvent was volatilized,
It was passed at a speed of 3 m / min under a high-pressure mercury lamp having an intensity of 80 W / cm set at a height of 12 cm from the coated surface. The coating was completely cured. Table 1 shows the performance test results of the obtained coating films.

Comparative Example 2 One side of a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm (“Lumirror” manufactured by Toray Industries, Inc.) was subjected to a dispersing and pulverizing treatment with 21 parts by weight of dipentaerythritol hexaacrylate, 9 parts by weight of N-vinylpyrrolidone. Silica powder ("Syloid" 2 manufactured by Fuji Devison Chemical Co., Ltd.)
44, an average particle diameter of 3.5 μm) A composition obtained by stirring and mixing 10 parts by weight of toluene, 40 parts by weight of toluene and 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone was applied using a bar coater to a cured film thickness of 3 μm. This was cured in the same manner as in Example 2 and the performance test results of the resulting coating film are shown in Table 1.

Examples 6 to 8, Comparative Example 3 A biaxially stretched polyethylene terephthalate film ("Lumirror" manufactured by Toray Industries, Inc.) having a thickness of 100 m was coated on one side with 60 parts by weight of dipentaerythritol hexaacrylate and a polyester acrylate (Aronix M manufactured by Toagosei Chemicals Co., Ltd.). −
7100) 30 parts by weight, tetrahydrofurfuryl acrylate
10 parts by weight, silica and butyral resin in the silica dispersion obtained in the same manner as in Example 1 were used in the amounts shown in Table 1, 2.5 parts by weight of silica powder (OK-412 manufactured by Degussa), 40 parts by weight of toluene, 1- A composition obtained by stirring and mixing 5 parts by weight of hydroxycyclohexyl phenyl ketone was applied using a bar coater so that the cured film thickness became 3 μm. This was left in a hot air dryer at 80 ° C for 30 seconds to evaporate the solvent, and 12 cm from the coated surface
At a speed of 3 m / min under a high-pressure mercury lamp having an intensity of 80 W / cm set at a height of 3 m / min. The coating was completely cured.

 Table 1 shows the performance test results of the obtained coating films.

Example 9 The following composition was synthesized by a conventional method.

100 parts by weight of dimethyl terephthalate, 75 parts by weight of dimethyl isophthalate, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate, 95 parts by weight of ethylene glycol, 85 parts by weight of neopentyl glycol, 0.106 parts by weight of manganese acetate tetrahydrate, 2 parts of calcium acetate After mixing 0.07 parts by weight of water salt and distilling methanol under a nitrogen stream at 140 to 220 ° C. and performing a transesterification reaction, 0.09 parts by weight of trimethyl phosphate and 0.06 parts by weight of antimony trioxide were added, and the mixture was heated from 240 ° C. 280 ℃
The temperature was raised over 1 hour and 30 minutes and the pressure was gradually lowered from normal pressure to 0.5 mmHg, excess diol components were removed from the system, and a polycondensation reaction was performed while maintaining this state for another 40 minutes.
A hydrophilic group-containing polyester copolymer having a glass transition temperature of 62 ° C. and an intrinsic viscosity [η] of 0.60 was obtained. Next, this copolymer 25
A mixture of 0 parts by weight and 110 parts by weight of butyl cellosolve is heated to 150 ° C.
For 4 hours to obtain a homogeneous solution. 480 parts by weight of water was gradually added dropwise to the resulting solution under high-speed stirring to obtain a uniform milky white opaque dispersion having a solid concentration of 25% by weight.

100 parts by weight of water was added to 70 parts by weight of the dispersion obtained above, and further 30 parts by weight of water, 1.5 parts by weight of benzoyl peroxide, 12 parts by weight of methyl methacrylate, and 2.5 parts by weight of polyoxyethylene alkyl ether phosphate ester. Was added thereto, and the mixture was stirred under a nitrogen gas flow for 1 hour, and then heated to 75 ° C. Next, a mixture of 40 parts by weight of methyl methacrylate, 30 parts by weight of ethyl acrylate, and 15 parts by weight of glycidyl methacrylate as the acrylic compound to be grafted was dropped into the above-prepared solution maintained at 85 ° C. with stirring over 60 minutes. Then, stirring was continued at 85 ° C. for 120 minutes under a nitrogen stream to obtain a water-dispersed graft copolymer having a solid content of 27% by weight. The graft ratio of the graft copolymer was 44%
Met.

 Next, a polyester laminate was produced by the following method.

First, a polyethylene terephthalate homopolymer chip (intrinsic viscosity = 0.62) manufactured by a conventional method was sufficiently dried in vacuum, fed to an extruder, melt-extruded at 280 ° C., and passed through a 10 μm cut metal sintered filter. rear,
Extruded into a sheet from a T-shaped die, and the surface temperature was 50 ° C.
And cooled and solidified. In order to improve the adhesion between the sheet and the surface of the cooling drum during this time, a wire electrode was arranged on the sheet side, and a DC voltage of 6000 V was applied. The unstretched polyethylene terephthalate film thus obtained was stretched 3.5 times in the longitudinal direction with a group of rolls heated to 95 ° C. to obtain a uniaxially stretched film. One surface of this film was subjected to a corona discharge treatment in a carbon dioxide gas atmosphere.

Then, an aqueous dispersion of the graft polymer prepared above and a melamine-based cross-linking agent “Nicalac” MW12LF as a cross-linking agent were used.
5 parts by weight of a cross-linking agent was mixed with 100 parts by weight of a graft polymer (manufactured by Sanwa Chemical Co., Ltd.) at a solids weight ratio, and further diluted with water to a solids concentration of 5.0% by weight. A coating was prepared by adding 0.5 parts by weight of colloidal silica having an average particle diameter of 0.10 μm to 100 parts by weight of the resin solid content.

Next, the coating agent was applied to the discharge-treated surface of the above-described uniaxially stretched film using a rod coater such that the coating film thickness after biaxial stretching was 0.08 μm.

The uniaxially stretched film after application is guided into a tenter, and the section from the inlet temperature of 150 ° C. to the stretching step is dehumidified stepwise while the coating film is dried. It was stretched 3.5 times. Further heat treatment at 240 ° C for 5 seconds with 2% relaxation, and modified layer thickness 0.08μm
Were laminated to obtain a plastic laminate having a thickness of 100 μm.

The crosslinked modified layer was molecularly oriented, and the presence of the hydrophilic group-containing polyester at a depth of up to 100 ° from the surface of the crosslinked modified layer was below the detection limit by the ESCA method.

Example 10 70 parts by weight of dipentaerythritol hexaacrylate, 30 parts by weight of N-vinylpyrrolidone, 10 parts by weight of silica particles obtained by dispersing the silica dispersion obtained in Example 1 on the undercoated surface of the polyethylene terephthalate film obtained in Example 9 A composition obtained by stirring and mixing 2.5 parts by weight of silica powder (OK-412), 40 parts by weight of toluene, and 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone with a roll coater has a thickness of 3 μm after curing using a roll coater. Was applied as follows. After drying at 80 ° C for 30 seconds, 80W /
It was passed under a high-pressure mercury lamp having an intensity of 3 cm at a speed of 3 m / min. The coating was completely cured.

This laminate had an abrasion resistance and adhesion rank of S3 and A5, and a flexibility of 4 mmφ. The haze was 25% and the 60 ° gloss was 45. In addition, the laminate had a boiling water resistance of rank A5, in which no abnormal appearance such as cracking was observed at all, and there was no decrease in adhesiveness of the cured layer. After 240 hours of the moist heat resistance test, the characteristics were examined. As a result, no abnormality such as cracks in the appearance was observed, and neither the abrasion resistance nor the adhesiveness of the cured film was reduced.

Example 11 80 parts by weight of methyl methacrylate, ethyl acrylate
10.8 parts by weight, 2-hydroxyethyl methacrylate 9.0
Parts by weight, 0.2 parts by weight of mono (3-chloro-2-hydroxypropyl methacrylate) acid phosphate, 67 parts by weight of toluene, 56 parts by weight of ethyl acetate, and 1.0 part by weight of azobisisobutyronitrile were mixed and melted, and the mixture was melted at 85 ° C. The reaction was performed for 5 hours.

To 100 parts of the above reaction product, 8 parts of "Sumidur N-75" (a 75% solution of trimer of hexamethylene diisocyanate, manufactured by Sumitomo Bayer) was added and mixed well.
By diluting with methyl isobutyl ketone (1: 1), a 10% non-volatile primer paint was prepared. Paint viscosity 3 at 25 ° C
It was centipoise.

One side of a 100 μm-thick biaxially stretched polyethylene terephthalate film (“Lumirror” manufactured by Toray Industries, Inc.) is coated with the paint prepared above using a roll coater so that the solid content is 0.3 g / m ^2. After drying and curing at 150 ° C. for 2 minutes, a polyethylene terephthalate film with a primer layer undercoated was obtained.

Example 12 Pentaerythritol triacrylate was applied to the undercoated surface of the obtained polyethylene terephthalate film.
70 parts by weight, 20 parts by weight of 1,6-hexanediol diacrylate, 10 parts by weight of N-vinylpyrrolidone, the silica dispersion obtained in Example 1 in an amount of 10 parts by weight of silica particles, silica powder (Fuji Devison Chemical Co., Ltd.) SYLOID 308) 2.5 parts by weight, 1-hydroxycyclohexyl phenyl ketone 5
A composition obtained by stirring and mixing 40 parts by weight of ethyl acetate and 40 parts by weight of ethyl acetate was applied using a bar coater so that the film thickness after curing became 3 μm. After drying at 80 ° C. for 30 seconds, the film was passed under a high-pressure mercury lamp having an intensity of 80 W / cm set at a height of 12 cm from the coated surface under a N ₂ atmosphere at a speed of 5 m / min. The coating was completely cured.

The abrasion resistance and adhesiveness ranks of this laminate were S3 and A5, and the flexibility was 4 mmφ. The haze was 26% and the 60 ° gloss was 41. In addition, the laminate had a boiling water resistance of rank A5, in which no abnormal appearance such as cracking was observed at all, and there was no decrease in adhesiveness of the cured layer. After 240 hours of the moist heat resistance test, the characteristics were examined. As a result, no abnormality such as cracks in the appearance was observed, and neither the abrasion resistance nor the adhesiveness of the cured film was reduced.

[Effects of the Invention] The present invention provides a radiation-curable composition comprising a flexible plastic layer and a composition in which specific silica particles and a butyral resin are mixed in a specific ratio with a specific monomer. By providing the hardened layer, a laminate having excellent surface hardness, scratch resistance, abrasion resistance, flexibility, and excellent non-glare properties can be obtained.

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Claims (3)

(57) [Claims] 1. A plastic laminate comprising a flexible plastic layer (I) and a radiation-cured layer (II) laminated in this order, wherein the radiation-cured layer (II) is three or more per molecule. At least one monomer (A) having a (meth) acryloyloxy group and at least one monomer (B) having one to two ethylenically unsaturated double bonds in one molecule. Of a radiation-curable composition comprising a radiation-curable monomer and a silica particle dispersion having an average particle diameter of 0.5 to 2.5 μm, which has been dispersed and pulverized in an organic solvent in which a dispersion stabilizing resin has been previously dissolved. A plastic laminate, which is a cured layer. 2. The composition according to claim 1, wherein the ratio of the monomers in the composition is 20 to 20%.
The plastic laminate according to claim 1, wherein the amount is 90% by weight and the monomer (B) is 10 to 80% by weight. 3. The plastic laminate according to claim 1, wherein the amount of the silica particles in the composition is 3 to 25 parts by weight based on 100 parts by weight of the monomer mixture.