JP6481565B2 - Hard coating agent for decorative film, cured film, plastic film, and molded product - Google Patents

Description

The present invention provides a hard coating agent for a decorative film, a hard film for a decorative film, which has excellent cured film elongation at the time of heating, and can impart excellent scratch resistance and chemical resistance after heat molding processing. The present invention relates to a cured film obtained by curing a coating agent and a plastic film obtained by laminating a cured film.

Conventionally, decoration techniques using decorative films have been widely used for surface decoration of articles such as electrical appliances, automobile exteriors, automobile interior parts, and daily necessities from the viewpoint of mass productivity and production cost. In-mold simultaneous decoration molding is mainly used, in which a decorative film is inserted and the surface of the plastic molded product is decorated at the same time as injection molding, but the decorative film is bonded to a molded product such as plastic, metal or glass, Or, the vacuum pressure bonding method to transfer the pattern or hard coat layer laminated on the decorative film has been proposed, and the decoration object and shape adaptability have further expanded, so the decorative film has a complicated shape and deep drawing process High elongation is required to follow (called deep drawing), and workability that does not cause cracks or the like even when the decorative film is stretched to 100% or more is required.

In any of these methods, a hard coat layer is provided on the outermost surface of the molded product for the purpose of protecting the design and maintaining a beautiful appearance for a long period of time in addition to the design properties by the pattern ink. For the hard coat layer, thermoplastic resins, thermosetting resins, and active energy ray-curable resins are used awards. Thermoplastic resins are excellent in processability but weak in chemical resistance, and thermosetting resins are processed. The active energy ray-curable resin is excellent in scratch resistance and chemical resistance, but has poor processability when cured before molding and is cured after molding. In this case, the production efficiency decreases due to poor handling and an increase in the number of steps of irradiating the molded product with active energy rays.

For these, Patent Document 1 proposes both workability and cured film physical properties by two-component curing of an active energy ray polymer having a hydroxyl group and a (meth) acryloyl group and a polyfunctional isocyanate ( Patent Document 1). However, it does not reach the workability required by the vacuum pressure bonding method. Further, it is necessary to irradiate the surface of the molded product after processing and molding with an active energy ray to form a cured film. However, in the case of a complicated shape, it is difficult to uniformly irradiate the entire surface, and productivity is poor.

Patent Document 2 proposes a resin composition comprising a compound having a total of two or more active methylene groups and / or active methine groups in one molecule, a compound having a (meth) acryloyl group, and a photopolymerization initiator. (See Patent Document 2). However, as in Patent Document 1, it is necessary to cure by active energy ray irradiation after processing and molding, and workability and productivity are poor.

Patent Document 3 also proposes a method of imparting processability by blending a non-reactive resin having no radical polymerizable double bond with a (meth) acrylic monomer (see Patent Document 3). However, when such a non-reactive resin or plastic resin is blended, it becomes flexible and processability is improved, but there is a tendency that scratch resistance and chemical resistance are insufficient.

In patent document 4, the method of controlling a crosslinking density by the compounding composition of the trifunctional or more than trifunctional (meth) acryl oligomer and the mono- or bifunctional (meth) acryl monomer is mentioned (refer patent document 4). According to this method, a hard coat film having both high surface hardness and flexibility capable of following deformation during molding can be obtained, but it has been difficult to achieve both high levels of surface hardness and elongation.

JP-A-10-58895 JP 2005-206778 A JP 2008-208154 A JP 2011-148964 A

The present invention is capable of forming a complex shape or deep drawing without cracking in processing and molding by vacuum pressure bonding, and is difficult to be scratched even though post-curing by active energy ray irradiation is not required after molding. It is to provide a hard coating agent for decoration having excellent sheath chemical resistance.

That is, the present invention 1 is obtained by radical polymerization of an ethylenically unsaturated monomer (a-1) having a site capable of coordination bonding and another ethylenically unsaturated monomer (a-2). A thermosetting resin composition comprising a copolymer (A) having a weight average molecular weight of 5,000 to 100,000 and a metal compound (B) capable of coordinating bonding, and comprising a cured film of the thermosetting resin composition It is a hard coating agent for a decorative film having a glass transition temperature of 80 to 150 ° C.

The present invention 2 relates to the present invention 1, wherein the ethylenically unsaturated monomer (a-1) having a site capable of coordinating bonding has at least one functional group selected from a hydroxyl group, a carboxyl group and an acetoacetyl group. It is a hard coating agent for a decorative film which is a compound contained in the molecule.

Invention 3 is a hard coating agent for a decorative film according to Invention 1 or 2, wherein the metal compound (B) is a metal chelate compound and / or a metal chelate compound of a metal alcoholate.

The present invention 4 is a cured film obtained by curing the hard coating agent for a decorative film according to any one of the present invention 1 to 3 by heat treatment.

The present invention 5 is a laminated plastic film having the cured film of the present invention 4.

The present invention 6 is a molded product obtained by coating the surface of the cured film of the present invention 4.

If the hard coating agent for a decorative film of the present invention is used, even in a cured film after a thermosetting reaction, the processability is good because it exhibits a cured film elongation of 100% or more at the time of heat processing molding, and after molding. The cured film is hard to be damaged, and a cured film having good chemical resistance can be obtained. Thereby, the hard coating agent for decorating which was difficult conventionally and does not require the hardening process after shaping | molding and was compatible with workability and the physical property of a coating film can be provided.

The present invention relates to an ethylenically unsaturated monomer (a-1) having a site capable of coordination bonding (hereinafter referred to as “component (a-1)”) and another ethylenically unsaturated monomer (a -2) Copolymer (A) (hereinafter referred to as “component (A)”) having a weight average molecular weight of 5,000 to 100,000 obtained by radical polymerization of (hereinafter referred to as “component (a-2)”) ) And a metal compound (B) capable of coordination bonding (hereinafter referred to as “component (B)”), and the glass transition temperature of the cured film of the thermosetting resin composition is 80. It is a hard coating agent for a decorative film having a temperature of ˜150 ° C.

The site capable of coordinate bonding is a chemical structure capable of having an unshared electron pair, and for a decorative film containing the component (A) having such a site and the component (B) described later. By using a hard coating agent, a cured film having excellent coating film elongation can be obtained when heated at 100 to 150 ° C. This makes it possible to obtain a cured film with excellent scratch resistance and chemical resistance in the cold state after molding. And film strength can be achieved.

The component (a-1) is preferably a compound having in the molecule at least one functional group among a hydroxyl group, a carboxyl group and an acetoacetyl group. Specific examples include at least one selected from the group consisting of a hydroxyl group-containing ethylenically unsaturated monomer, a carboxyl group-containing ethylenically unsaturated monomer, and an acetoacetyl group-containing ethylenically unsaturated monomer. Thereby, it can be set as the hardened | cured material which used the (B) component as the crosslinking agent. Among these, an acetoacetyl group-containing ethylenically unsaturated monomer and / or a carboxyl group-containing ethylenically unsaturated monomer are particularly preferred from the viewpoint of excellent solvent resistance with respect to cured properties.

Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) Acrylate, butanediol mono (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol Lumpur (meth) acrylate, 1,4-sill b hexane dimethanol monoacrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl swine rate, and the like. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of easy availability.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, (meth) acrylic acid dimer, (meth) acrylic acid trimer, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth). Examples include acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-acryloyloxypropyl hexahydrophthalate, and EO-modified succinic acid (meth) acrylate. Among these, (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalate, and EO-modified succinic acid (meth) acrylate are preferable from the viewpoint of easy availability.

Examples of the acetoacetyl group-containing ethylenically unsaturated monomer include acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, and acetoacetoxybutyl (meth) acrylate. Among these, acetoacetoxyethyl (meth) acrylate is preferable from the viewpoint of easy availability.

Representative examples of the component (a-2) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) ) Acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate Rate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, methoxydipropylene glycol (meth) Acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, noniephenoxypolyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, isobornyl (meth) acrylate , Phenoxydiethylene glycol (meth) acrylate, and styrene. These ethylenically unsaturated monomers can be used alone or in combination of two or more. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, and styrene are preferred because the cured film is less likely to crack during processing and the cured film surface is less likely to be damaged.

The copolymer (A) is obtained by radical polymerization of the components (a-1) and (a-2), and the copolymerization ratio of the components (a-1) and (a-2). Is not particularly limited as long as the weight average molecular weight of the component (A) is in the range of 5,000 to 100,000, but the weight ratio of the component (a-1) to the component (a-2) is preferably 10: It is about 90-80: 20. (A-1) When the ratio of a component is less than 10, the chemical resistance of a cured film will fall. On the other hand, when it exceeds 80, the viscosity of the component (A) becomes high and handling becomes difficult. (A) The radical copolymer of a component can be synthesized by a conventionally known synthesis method such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method or a bulk polymerization method. In particular, the solution polymerization method is preferable because of easy control of the molecular weight.

When the component (A) is produced by the solution polymerization method, the component (a-1) and the component (a-2) are used as raw materials, an organic solvent is added, and a radical polymerization initiator is further added. It is obtained by holding at 50 to 150 ° C. for 2 to 12 hours. Since the radical polymerization initiator species and the reaction temperature can affect the weight average molecular weight of the component (A) to be generated, it is necessary to adjust the radical polymerization initiator species and the reaction temperature to be in an arbitrary weight average molecular weight range.

As said radical polymerization initiator, a well-known thing can be used without limitation. Specifically, for example, inorganic peroxides such as hydrogen peroxide, ammonium persulfate and potassium persulfate, organic peroxides such as benzoyl peroxide, dicumyl peroxide and lauryl peroxide, 2,2′-azobis And azo compounds such as isobutyronitrile and dimethyl-2,2′-azobisisobutyrate. These may be used alone or in combination of two or more. In addition, although the usage-amount of a radical polymerization initiator is not specifically limited, Since it may affect the weight average molecular weight of the copolymer copolymer (A) to produce | generate, the copolymer polymer (weight average molecular weight 5,000-100,000 ( In order to achieve A), it is preferable that the amount be about 0.01 to 8 parts by weight with respect to 100 parts by weight of the total polymerization components. In addition, you may use a chain transfer agent etc. as needed.

Examples of the chain transfer agent include n-lauryl mercaptan, n-dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and the like. These may be used alone or in combination of two or more. The amount of the chain transfer agent used is preferably about 0.01 to 5 parts by weight with respect to 100 parts by weight of all the polymerization components used.

About the solvent at the time of solution polymerization mentioned above, if it is an organic solvent compatible with (a-1) component, (a-2) component, and (A) component, it can be especially used without a restriction | limiting. Preferably, it is possible to maintain a suitable reaction temperature of 50 ° C. to 150 ° C. during the radical polymerization reaction, and those having good volatility during drying of the coating liquid are preferred. Methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, acetic acid Ethyl, butyl acetate, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, diacetone alcohol, acetylacetone, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, n-heptane, Isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Seteto and the like, can also be used in one or more mixing liquid. Of these, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, diacetone alcohol, acetylacetone, and propylene glycol monomethyl ether are preferred from the viewpoints of drying property particularly suitable for coating and odor during drying. The amount of the organic solvent used is usually 60 to 150 parts by weight with respect to 100 parts by weight of the raw material solid content.

By setting the weight average molecular weight of the synthesized component (A) to 5,000 to 100,000, the cured film properties and handling can be improved. When the weight average molecular weight is less than 5,000, the chemical resistance of the cured film is lowered. On the other hand, when it exceeds 100,000, the viscosity becomes high, and the handling becomes worse due to the tendency of the poor compatibility with the organic solvent.

As the component (B), various known compounds can be used without particular limitation as long as they are metal compounds having coordination ability. Specific examples include at least one selected from the group consisting of metal chelate compounds, metal alcoholates, and metal acylates. The metal chelate compound includes a partial alcoholate or partial acylate thereof, the metal alcoholate includes a hydrolyzate or condensate thereof, and the metal acylate includes a hydrolyzate or condensate thereof. . Among these, metal chelate compounds and / or metal chelate compounds of metal alcoholates are preferable from the viewpoint of storage stability.

Examples of the metal constituting the component (B) include aluminum, zirconium, titanium, magnesium, chromium, cobalt, copper, iron, nickel, vanadium, zinc, indium, calcium, manganese, and tin. Among these, aluminum, zirconium and titanium are preferable from the viewpoint of easy availability as the component (B).

Examples of the metal chelate compound include aluminum ethyl acetoacetate / diisopropylate, alkyl acetoacetate aluminum diisopropylate, aluminum trisethyl acetoacetate, aluminum monoacetyl acetate bisethyl acetoacetate, aluminum trisacetylacetonate, aluminum monoisopropylate. Aluminum compounds of propoxy mono-oroxyethyl acetoacetate; zirconium compounds such as zirconium tetraacetyl acetate, zirconium tributoxy monoacetyl acetate, zirconium monobutoxy acetyl acetate bisethyl acetoacetate, zirconium dibutoxy bisethyl acetoacetate; titanium diisopropoxy bis Acetyl acetate, titanium Titanium compounds such as laacetyl acetate, titanium dioctyloxybisoctylene glycolate, titanium diisopropoxybisethyl acetoacetate; ethoxy acetylacetonate zinc, bisacetylacetonate zinc, propoxy acetylacetonate zinc, butoxy acetyl Zinc compounds such as acetonate zinc, ethoxy / ethyl acetoacetate zinc, bisethyl acetoacetate zinc, propoxy / ethyl acetoacetate zinc, butoxy / ethyl acetoacetate zinc are listed.

Examples of the metal alcoholate include aluminum ethylate, aluminum propylate, aluminum isopropylate, aluminum diisopropylate monosec butyrate, aluminum monoisopropylate disec butyrate, aluminum compound of aluminum sec butyrate; diethoxy zinc, dipropoxy zinc, Zinc compounds such as dibutoxy zinc, titanium compounds such as titanium ethylate, titanium propyrate, titanium isopropylate, and titanium butyrate; zirconium compounds such as zirconium ethylate, zirconium propyrate, zirconium isopropylate, and zirconium butyrate . Examples of the condensate of the metal alcoholate include cyclic aluminum oxide isopropylate, cyclic aluminum oxide octylate, and cyclic aluminum oxide stearate.

Examples of the metal acylate include zirconium monopropyl tristearate, zirconium dipropyl distearate, zirconium tripropyl monostearate, zirconium monobutoxy tristearate, zirconium dibutoxy distearate, zirconium tributoxy monostearate and the like. And the condensate includes polyhydroxytitanium stearate.

Although the usage-amount of said (B) component is not specifically limited, By setting about 0.25-3 mol with respect to 3 mol of (a-1) component in (A) component, it shall be favorable cured film physical property. Can do. By setting the amount of component (B) used to be 0.25 mol or more, the cured film will exhibit good cured film properties including curability, and by setting it to 3 mol or less, the storage stability of the coating agent is increased. Will be better.

In addition to the (A) component and the (B) component, the hard coating agent for a decorative film of the present invention is an organic solvent for adjusting the dilution to a viscosity suitable for coating, for improving the coating appearance. Additives, inorganic fillers or organic fillers for improving coating film properties can be used.

The organic solvent for dilution adjustment is not particularly limited as long as it is an organic solvent having good compatibility with the components (A) and (B) and has good volatility when drying the coating liquid. Specifically, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, diacetone alcohol , Acetylacetone, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane, propylene glycol monomethyl ether, ethylene glycol monoethyl ether Tate, propylene glycol monomethyl ether acetate. These may be used alone or in combination of two or more. In general, the blending amount is adjusted so that the coating liquid viscosity is about 5 to 1000 mPa · s.

As the additive, commercially available silicones, acrylics, fluorine leveling agents, and surface conditioners can be used. For example, BYK 300 series, BYK-UV 3500 series, BYKETOL-OK, etc. of BYK company can be used.

Examples of the inorganic filler include particles of metal oxides such as silica, alumina, zirconia, and titania, and particles, plates, scales, or fibers of glass. Examples of the organic filler include organic beads composed of methacrylic acid ester polymers, polyurethane, polystyrene, and carbon nanotubes, and carbon nanotubes are used without particular limitation as long as they do not impair the transparency of the cured film. I can do it.

Furthermore, commercially available antioxidants, ultraviolet absorbers, scratch inhibitors, slip agents, antiblocking agents, and the like can be used without particular limitation depending on the application.

A cured film obtained by curing a hard coating agent for a decorative film by heat treatment is also one aspect of the present invention. By this heat treatment, the organic solvent that can be contained in the decorative film hard coating agent is volatilized and the cured reaction proceeds to obtain a cured film. This heat treatment is preferably performed at a temperature of 80 ° C. to 160 ° C. for 30 seconds to 10 minutes. Thereby, the glass transition temperature of a cured film can be 80 to 150 degreeC.

By heating the hard coating agent for decoration at a temperature higher than 80 ° C., the curing reaction sufficiently proceeds, and the solvent in the cured film is sufficiently volatilized. By heating at a temperature lower than 160 ° C., it is possible to prevent heat denaturation from occurring in the plastic film described later. The heat treatment time is usually 30 seconds to 10 minutes, and a high temperature of 120 ° C. to 160 ° C. is preferable from the viewpoint of productivity. Thereby, the curing reaction is completed in a short time of about 30 seconds to 3 minutes. On the other hand, when the temperature setting is 80 ° C. to 120 ° C., a heating time of about 5 minutes to 10 minutes is required.

The glass transition temperature (Tg) of the cured film thus obtained can be measured by collecting only the cured film and analyzing the difference in calorie from the reference material by differential scanning calorimetry. Generally, the cured film has a heat of 140 ° C. to 180 ° C. applied to the decorative film at the time of molding. Therefore, by setting the Tg of the cured film to a range of 80 ° C. to 150 ° C., the cured film is heated by the heat at the time of molding. Softens and can exhibit sufficient elongation at the time of molding. When the Tg of the cured film is 80 ° C. or lower, physical properties of the coating film such as difficulty of scratching and chemical resistance are deteriorated. On the other hand, when the temperature is 150 ° C. or higher, the cured film cannot be softened by heat during molding, and cracks are generated.

A plastic film in which this cured film is laminated is also one aspect of the present invention. Examples of the plastic film include polyethylene terephthalate, polycarbonate, polypropylene, polyethylene, polyolefin, polystyrene, polyamide, polyester, etc. Among them, polyethylene terephthalate is preferable because it is easily available on the market.

The decorative hard coating agent of the present invention is applied to a plastic substrate by the gravure coating method, roll coating method, spray coating method, comma coating method, lip coating method, gravure printing method, screen printing method, etc. and heated. The cured film can be laminated with. The gravure printing method is preferred from the viewpoint of productivity. Moreover, it is preferable from the point of the physical property of a cured film to coat so that the thickness of a cured film may be set to 3-10 micrometers by the gravure printing method.

Depending on the application of the decorative film, the surface of the plastic film is subjected to easy adhesion treatment for the purpose of improving adhesion to the cured film of the present invention, or peeling treatment to facilitate peeling of the cured film from the plastic film. May be.

The easy adhesion treatment may be performed by corona treatment, plasma treatment, or a resin having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a polyamide skeleton, a polyvinyl alcohol skeleton, or the like alone or in combination of two or more. It can be done by laminating an easy adhesion layer.

The above peeling treatment is not particularly necessary when the peelability is good, but in order to make peeling easier, melamine resin, silicone resin, fluororesin, cellulose derivative, urea resin, polyolefin resin These can be laminated as a release layer by combining one or more of these paraffinic resins.

Next, a molded product formed by laminating the cured film of the present invention will be described. This molded product is also one aspect of the present invention. The cured film of the present invention can be laminated on the surface of the molded product by using a method such as the in-mold simultaneous decorating method or the vacuum pressure method. And a transfer method in which only a cured film or other patterned ink layer or functional layer laminated on a plastic film is transferred to the surface of the molded product.

In the above laminating method, the decorative film is generally composed of the cured film layer of the present invention, the anchor layer, the handle ink layer, the easy-adhesion layer, the plastic film, the functional layer, the adhesive layer, or the cured film of the present invention. There are layer configurations such as a layer, an easy-adhesion layer, a plastic film, an easy-adhesion layer, a pattern ink layer, a functional layer, and an adhesive layer, and can be bonded to the surface of the molded product via the adhesive layer.

In the above transfer method, a release layer is generally laminated on a plastic film, if necessary, and the cured film layer, anchor layer, handle ink layer, functional layer, and adhesive layer of the present invention are laminated in that order. After being attached to the surface of the molded product via an adhesive layer, the plastic film or the layer between the release layer and the cured film layer is peeled off, and only the transfer layer is applied to the surface of the molded product. Can be laminated.

Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to these examples. In the following description, parts and% are based on weight.

<Synthesis Example 1>
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet, and dropping funnel was charged with 47.6 parts of methyl isobutyl ketone (hereinafter referred to as MIBK). The temperature was raised to. Subsequently, a mixed solution comprising 38.1 parts of methyl methacrylate (hereinafter referred to as MMA), 9.5 parts of methacrylic acid-2-hydroxyethyl (hereinafter referred to as HEMA), and 4.8 parts of azobisisobutyronitrile (hereinafter referred to as AIBN). Was added dropwise from a dropping funnel over 2 hours and reacted at 110 ° C. for 12 hours in a nitrogen atmosphere to obtain 100 g of a copolymer polymer solution having a resin content of 50%. This copolymer was designated as (A-1), and the weight average molecular weight (polystyrene equivalent value by GPC) was 6,000. The weight average molecular weight was obtained by connecting three gel permeation chromatography (manufactured by Tosoh Corporation, trade name “HLC-8220”, column: Tosoh Corporation, trade name “TSKgel superHZ-M” in series. The measured values are shown below (the same applies hereinafter).

<Synthesis Example 2>
48.8 parts of MIBK was charged into the same reaction vessel as in Synthesis Example 1, and the temperature was raised to 90 ° C. while stirring. Next, a mixed solution consisting of 39.0 parts of MMA, 9.8 parts of HEMA, and 2.4 parts of AIBN was dropped from the dropping funnel over 2 hours, and the mixture was reacted at 90 ° C. for 12 hours in a nitrogen atmosphere to give a resin content of 50%. 100 g of a copolymer solution was obtained. This copolymer was designated as (A-2), and the weight average molecular weight was 13,000.

<Synthesis Example 3>
48.8 parts of MIBK was charged into the same reaction vessel as in Synthesis Example 1, and the temperature was raised to 90 ° C. while stirring. Next, a mixed liquid consisting of 24.4 parts of MMA, 12.2 parts of cyclohexyl methacrylate (hereinafter referred to as CHMA), 12.2 parts of methacrylic acid, and 2.4 parts of AIBN was dropped from the dropping funnel over 2 hours, and the reaction was performed in a nitrogen atmosphere. At 90 ° C. for 12 hours to obtain 100 g of a copolymer solution having a resin content of 50%. This copolymer was designated as (A-3), and the weight average molecular weight was 14,000.

<Synthesis Example 4>
In a reaction vessel similar to Synthesis Example 1, 49.9 parts of propylene glycol monomethyl ether (hereinafter referred to as PM) was charged and heated to 80 ° C. with stirring. Next, a mixed solution consisting of 15.0 parts of ethyl methacrylate (hereinafter referred to as EMA), 34.9 parts of 2-acetoacetoxyethyl methacrylate (hereinafter referred to as AAEM) and 0.3 part of AIBN was dropped over 2 hours from the dropping funnel. The mixture was reacted at 0 ° C. for 12 hours in a nitrogen atmosphere to obtain 100 g of a copolymer polymer solution having a resin content of 50%. This copolymer was designated as (A-4), and the weight average molecular weight was 62,000.

<Synthesis Example 5>
48.8 parts of MIBK was charged into the same reaction vessel as in Synthesis Example 1, and the temperature was raised to 80 ° C. while stirring. Next, a mixed solution composed of 24.4 parts of MMA, 24.4 parts of AAEM, and 2.4 parts of AIBN was dropped from the dropping funnel over 2 hours, and the mixture was reacted for 12 hours while refluxing in a nitrogen atmosphere to obtain a resin content of 50%. 100 g of a copolymer polymer solution was obtained. This copolymer was designated as (A-5), and the weight average molecular weight was 15,000.

<Synthesis Example 6>
In the same reaction vessel as in Synthesis Example 1, 49.4 parts of MIBK was charged, and the temperature was raised to 80 ° C. while stirring. Next, a mixed solution consisting of 34.6 parts of MMA, 14.8 parts of AAEM, and 1.2 parts of AIBN was dropped from the dropping funnel over 2 hours and reacted for 12 hours while refluxing in a nitrogen atmosphere, and the resin content was 50%. 100 g of a copolymer polymer solution was obtained. This copolymer was designated as (A-6), and the weight average molecular weight was 30,000.

<Synthesis Example 7>
In the same reaction vessel as in Synthesis Example 1, 47.6 parts of MIBK was charged, and the temperature was raised to reflux (MIBK boiling point 116 ° C.) while stirring. Next, a mixed solution composed of 38.1 parts of MMA, 9.5 parts of HEMA, and 4.8 parts of AIBN was dropped from the dropping funnel over 2 hours, and the mixture was reacted for 12 hours while refluxing in a nitrogen atmosphere to give a resin content of 50%. 100 g of a copolymer polymer solution was obtained. This copolymer was designated as (A-7), and the weight average molecular weight was 3,500.

<Synthesis Example 8>
In the same reaction vessel as in Synthesis Example 1, 45.8 parts of MIBK was charged, and the temperature was raised to 90 ° C. while stirring. Next, a mixed liquid consisting of 36.6 parts of MMA, 12.2 parts of glycidyl methacrylate (hereinafter referred to as GMA) and 2.4 parts of AIBN was dropped from the dropping funnel over 2 hours, and reacted at 90 ° C. for 18 hours in a nitrogen atmosphere. 100 g of a copolymer polymer solution having a resin content of 50% was obtained. This copolymer was designated as (A-8), and the weight average molecular weight was 22,000.

<Synthesis Example 9>
Into the same reaction vessel as in Synthesis Example 1, 43.2 parts of MIBK was charged, and the temperature was raised to 90 ° C. while stirring under a nitrogen stream, and then 32.4 parts of MMA, 10.8 parts of GMA, AIBN 2.2 in advance. The mixture was dropped from a dropping funnel charged with a portion of the mixture over 2 hours and reacted at 90 ° C. for 12 hours in a nitrogen atmosphere. Thereafter, the temperature was raised to 120 ° C., held for 4 hours, and then cooled to room temperature, 5.5 parts of acrylic acid (hereinafter referred to as AA), 0.1 part of triphenylphosphine, 0.2 part of methoquinone, and 5.63 parts of MIBK. And the nitrogen inlet was replaced with an air bubbling device and stirred while bubbling air and reacted at 110 ° C. for 6 hours to obtain 100 g of a copolymer polymer solution having a resin content of 50%. This copolymer was designated as (A-9), and the weight average molecular weight was 28,000.

<Synthesis Example 10>
As in Synthesis Example 1, 49.3 parts of PM was charged, and the temperature was raised to 85 ° C. while stirring. Next, a mixed solution consisting of 49.3 parts of MMA and 1.5 parts of AIBN was dropped from the dropping funnel over 2 hours and reacted at 85 ° C. for 12 hours in a nitrogen atmosphere to obtain 100 g of a copolymer polymer solution having a resin content of 50%. Obtained. This copolymer was designated as (A-10), and the weight average molecular weight was 48,000.

Next, examples of the hard coating agent for decoration of the present invention will be shown.
< Reference Example 1 >
40.3 parts of copolymer (A-1), 4.9 parts of aluminum trisethyl acetoacetate (hereinafter referred to as AL-T), and 54.8 parts of propylene glycol monomethyl ether (hereinafter referred to as PM) are stirred uniformly. Thus, a decorative hard coating agent having a solid content of 25% was obtained.

< Reference example 2, Examples 3-8 >
Hereinafter, similarly, according to the compounding ratio of Table 2, the hard coating agent for decoration was prepared.

AL-T: Aluminum trisethyl acetoacetate AL-M: Aluminum monoacetylacetonate bisethylacetoacetate 76% isopropanol solution Zr-T: Zirconium tetraacetylacetonate 20% toluene solution Ti-T: Titanium tetraacetylacetonate 65% 2-propanol solution Zr-B: zirconium butyrate 87% normal butanol solution Ti-B: titanium butyrate 99% normal butanol solution Filler: glass filler Asahi Glass Co., Ltd., center particle size 0.8 μm
AC: Acetylacetone

Table 3 shows the compositions of Comparative Examples 1 to 6 for the present invention.

Isocyanate: Product name "Coronate HX" manufactured by Nippon Polyurethane
PE3A: Pentaerythritol triacrylate SI-80L: Product name “SI-80L” manufactured by Sanshin Chemical Industry Co., Ltd.
Irg184: Product name “Irgacure 184” manufactured by BASF
MEK: Methyl ethyl ketone

The above-mentioned decorative hard coating agents of Reference Examples 1 and 2, Examples 3 to 8 and Comparative Examples 1 to 6 were coated on a highly adhesive polyethylene terephthalate film with a bar coater No. 20 was hand-coated to a dry film thickness of 5 μm and dried at 150 ° C. for 3 minutes.

<Production of cured film>
A cured film was obtained by further heat treatment at 150 ° C. for 10 minutes from the dry film states of Reference Examples 1 and 2, Examples 3 to 8, and Comparative Examples 1, 2, 4, and 5. In Comparative Examples 3 and 6, a cured film was prepared by irradiating an accumulated dose of 450 mJ / cm ² using a high pressure mercury lamp 80W and one lamp from the dry film state, and the following evaluation was performed.

<Glass transition temperature>
Only the cured film component was scraped from the surface of each cured film, and the glass transition temperature was measured with a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.).

<Elongation at coating time>
A test piece obtained by cutting a cured film film into a strip shape having a length of 100 mm and a width of 7 mm is set in a tensile tester (model number “AGS-10KNX”, Shimadzu Corporation) with a distance between chucks of 50 mm, under an environment at a room temperature of 150 ° C. The test was carried out at a pulling speed of 10 mm / min, stopped when the distance between chucks reached 150 mm (elongation 150%), and the presence or absence of cracks in the cured film was visually observed. If it did, it evaluated as x. By measuring the elongation of the cured film, the processability of the cured film when heated can be evaluated. If it is a cured film in which cracks do not occur when stretched by 150%, it is possible to obtain a molded product with a good cured film surface laminated without cracks even during actual molding. On the other hand, if it is a cured film in which cracks are caused by stretching by 150%, a molded product having cracks on the surface is obtained.

<Pencil hardness>
The pencil hardness was evaluated according to JIS-K-5600. Those having a pencil hardness of H or higher were regarded as having excellent hardness and sufficiently satisfying the hard coat property, and those having a pencil hardness of F or less were evaluated as being inferior in hard coat property.

<Chemical resistance>
Using three types of organic solvents, methanol, toluene, and acetone, each organic solvent was soaked in absorbent cotton, and the cured film surface was rubbed 10 times with a load of 4.9 N, and then the cured film surface before and after the test was applied. The thing which did not change was evaluated as (circle), and the thing with a change was evaluated as x. Furthermore, even after 100 reciprocating rubs, it was marked as ◎ if the cured film surface did not change.

Table 4 shows the evaluation results of Reference Examples 1 and 2, Examples 3 to 8, and Comparative Examples 1 to 6.

Claims (4)

Radical polymerization of an acetoacetyl group-containing ethylenically unsaturated monomer and / or a carboxyl group-containing ethylenically unsaturated monomer (a-1) and another ethylenically unsaturated monomer (a-2) A thermosetting resin composition comprising the resulting copolymer (A) having a weight average molecular weight of 5,000 to 100,000 and a metal chelate compound and / or metal alcoholate (B). The glass transition temperature of the cured film is 80 to 150 ° C. , and the amount of the component (B) used is 0.25 mol or more and 3.61 mol or less with respect to 3 mol of the component (a-1). Coating agent. A cured film obtained by curing the hard coating agent for a decorative film according to claim 1 by heat treatment. A plastic film formed by laminating the cured film according to claim 2 . A molded product obtained by coating the surface of the cured film according to claim 2 .