TWI572624B - A polyfunctional sulfur (meth) acrylate resin, an active energy ray-hardening hard coat resin composition containing the same, a hardened film obtained by hardening the plastic film, a plastic film having a hardened film, a plastic film And processed products - Google Patents

Description

A polyfunctional sulfur (meth) acrylate resin, an active energy ray-curable hard coat resin composition containing the same, a cured film obtained by curing the same, a plastic film laminated with a cured film, and a plastic injection molded product using a plastic film And processed products Field of invention

The present invention relates to a polyfunctional sulfur (meth) acrylate resin, an active energy ray-curable hard coat resin composition containing the same, a cured film obtained by hardening the same, a plastic film laminated with a cured film, and a plastic film. Plastic injection molded products and processed products.

Background of the invention

As a manufacturing method for decorating the surface of a plastic product with a pattern or a pattern and imparting scratch resistance, attention has been paid to: (1) In-mold decoration molding method (referred to as Film Insert Moulding, In-Mold Decorating, In -Mold Laminating, etc., which inserts a decorative hard coat film having an adhesive layer or a pattern layer and a hard coat layer on a plastic film such as PET (polyethylene terephthalate) into a mold. The film is attached to the plastic molded article at the same time as the injection molding; or (2) the film-bonding decorative method is applied to the surface of the molded plastic product, and the decorative hard coat film on the steel plate or the building material.

In the above method, the decorative hard coat film is stretched along the inner surface of the mold or the shape of the product of the molded article. However, in general, the hard coat layer is harder and the properties become harder and brittle. Therefore, the decorative hard coat film used in the above method is liable to cause cracks due to stress during stretching and is inferior in workability. Specifically, in the case of severe processing of a curved surface or box processing (ie, "deep processing"), cracks are likely to occur, and the hard coat property is lowered to provide flexibility to improve workability, or, in terms of design limit.

In recent years, in order to achieve product differentiation, design complication and scratch resistance of the surface are required, so that both the flexibility of the hard coat film and the hard coat property are indispensable. In this regard, various methods have been proposed. For example, a method of controlling the crosslinking density by a combination of a trifunctional or higher (meth)acryl fluorenyl oligomer and a mono-difunctional (meth) acrylonitrile-based monomer can be mentioned (see Patent Document 1). According to this method, a hard coat film having high surface hardness and flexibility (which can be deformed in conformity with molding) can be obtained, but surface hardness and flexibility are mutually exclusive relations, and there is a need to compromise to a certain extent. The problem under balance.

Further, as another example, a mixed (meth) acrylate polymer and a polyfunctional urethane (meth) acrylate having a molecular weight of 5,000 to 50,000 and a methyl group have been proposed. When the propylene oxime equivalent is 200 g/eq or more and 800 g/eq or less, the polyfunctional urethane (meth) acrylate has a molecular weight of 1,000 to 10,000 and the (meth) acrylonitrile equivalent is 100 g/eq or more and does not reach 200 g/eq (refer to Patent Document 2). However, even in this document, the balance of the two-phase trade-off between the hard coat layer and the softness is regulated by the (meth) acrylonitrile equivalent, and it has to be compromised to some degree of balance.

In addition, a method of providing a processability by mixing a non-reactive resin having no radically polymerizable double bond with a (meth)acrylonitrile-based monomer has been proposed (see Patent Document 3). However, in the case of such a non-reactive resin or a plastic resin, it is soft and the workability is improved, but it is difficult to achieve high hard coat properties required in recent years.

Prior technical literature Patent literature

Patent Document 1 is Japanese Patent Laid-Open No. 2011-148964.

Patent Document 2 is Japanese Laid-Open Patent Publication No. 2004-123780.

Patent Document 3 is Japanese Patent Laid-Open No. 2008-208154.

Summary of invention

An object of the present invention is to provide a polyfunctional sulfur (meth) acrylate resin which can form a cured film having a hard coat property and high flexibility and excellent workability.

That is, the present invention is a polyfunctional sulfur (meth) acrylate resin having two or more terminal structures represented by the following formula (1) and a polyfunctional thiol compound (A) (hereinafter also referred to as The thiol end of the component (A) and the (meth) acryloyl group at the terminal end of at least one side of the difunctional (meth) acrylate compound (B) (hereinafter also referred to as the component (B)) are subjected to the ene-sulfur The polyfunctional thiol compound (A) is calculated by the formula 1 and x is 100 or more and 200 or less:

(wherein, X represents a structure other than a terminal thiol group in the polyfunctional thiol compound (A). Each of R ₁ and R ₃ is hydrogen or a methyl group, and R ₂ represents O or -OR ₉ -O-. R ₉ is selected from at least one of the following: a linear or branched alkyl group of C1-20, -(CH ₂ CH ₂ O) _m CH ₂ CH ₂ -, -(CH ₂ CH(CH ₃ ) O) _m CH ₂ CH(CH ₃ )-, -CH ₂ CH ₂ OP=O(OH)OCH ₂ CH ₂ -, -CH ₂ CH(OH)CH ₂ -, and the following formula (1-1)~ (1-3) The structure shown. m, p, and q represent positive integers and p+q=2~6.)

Further, the present invention provides a polyfunctional sulfur (meth) acrylate resin having a terminal structure represented by the following formula (2), which is at least one of a thiol terminal and a component (B) of the component (A). The (meth) acrylonitrile group at the side end is bonded by an ene-thiol reaction.

(wherein, X represents a structure other than a terminal thiol group in the polyfunctional thiol compound (A). R ₁ and R ₃ each represent hydrogen or a methyl group, and R ₂ represents O or -OR ₉ -O-. R ₉ is selected from at least one of the following, a straight or branched alkyl group of C1-20, -(CH ₂ CH ₂ O) _m CH ₂ CH ₂ -, -(CH ₂ CH(CH ₃ ) O) _m CH ₂ CH(CH ₃ )-, -CH ₂ CH ₂ OP=O(OH)OCH ₂ CH ₂ -, -CH ₂ CH(OH)CH ₂ -, and the following formula (1-1)~ (1-3) The structure shown. m, p, and q represent positive integers and p+q=2~6.)

Further, in the present invention, in the first aspect of the invention, the component (A) is a polyfunctional sulfur (methyl) of any of the polyfunctional thiol compounds represented by the following formulas (3) to (7). Acrylate resin.

(wherein R ₄ represents hydrogen or a methyl group, and n represents an integer of 1 to 12.)

(wherein R ₅ represents hydrogen or methyl.)

(wherein R ₆ represents hydrogen or methyl.)

(wherein R ₇ represents hydrogen or methyl.)

(wherein R ₈ represents hydrogen or methyl.)

Further, the present invention provides an active energy ray-curable hard coat resin composition comprising: a polyfunctional sulfur (meth) acrylate resin according to any one of Inventions 1 to 3; and having three or more (meth) groups a polyfunctional (meth) acrylate of acrylonitrile; and a photopolymerization initiator.

Further, the present invention is a cured film obtained by irradiating an active energy ray-curable hard coat resin composition of the present invention 4 with an active energy ray and hardening it.

Further, the present invention 6 is a plastic film in which the cured film of the present invention 5 is laminated.

Further, in the seventh aspect of the invention, the plastic injection molded article of the plastic film of the invention 6 is used.

Further, the present invention 8 is a processed product in which the plastic film of the invention 6 is laminated.

When the thioether-bonded polyfunctional sulfur (meth) acrylate resin of the present invention is used, a cured film having both flexibility and excellent hard coat properties (excellent surface damage resistance) can be formed, and the film is excellent. The hard coat layer has high pencil hardness and scratch resistance. Thereby, a hard coat film can be formed which is excellent not only in the processability of the conventional technique but also in the case where the surface of the cured film is not easily damaged.

Form for implementing the invention

The component (A) in the present invention is not a monofunctional thiol compound, and is not particularly limited as long as it is a polyfunctional thiol compound having two or more thiol groups (-SH) as a reactive functional group at the terminal. By using the component (A) as a polyfunctional thiol compound, the resin of the present invention can be a polyfunctional sulfur (meth) acrylate resin having two or more (meth) acrylonitrile groups at the terminal, which is irradiated with an active energy ray. The hardened material obtained can easily obtain a dense three-dimensional crosslinked structure, so that it can have excellent hard coat properties. The polyfunctional sulfur (meth) acrylate resin in the present specification means a polyfunctional (meth) acrylate containing two or more thioether bonds.

Further, in the above component (A), the x calculated from the formula 1 is from 100 to 200, and from the viewpoint of producing a polyfunctional sulfur (meth)acrylate resin which forms a cured film having excellent hard coat properties, It is suitable. If x is from 100 to 200, a dense three-dimensional crosslinked structure can be obtained, and a more excellent hard coat property can be provided. As a specific example, it can be exemplified that it can be expressed by the general formula (3) to (7). Tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropoxy)-ethyl]-trimer A polyfunctional thiol compound, such as an isocyanate, a neopentyl tetrakis-tetramethyl propyl propyl acrylate, or a neopentyl pentoxide hexa(3-mercaptopropionate), may be used alone or in combination of two or more. From the viewpoint of easiness of availability, the polyfunctional thiol compound represented by the general formulae (3) to (7) is preferred.

The component (B) is not particularly limited as long as it has a (meth)acryloyl group at the terminal of at least one side. When a trifunctional or higher polyfunctional (meth) acrylate compound is used, in the reaction with an ene-thiol of a polyfunctional thiol compound, the cross-linking structure of the molecules is likely to be excessively formed, and as a result, gelation easily occurs. Reaction control becomes difficult. Specific examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and polyethylene glycol di(methyl). Acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene di(meth)acrylate, 1,3-butane II Alcohol (meth) acrylate, 1,4-butane diol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 2-(meth) propylene oxiranyl ethyl Acid phosphate, 3-methyl-1.5-pentane diol di(meth) acrylate, 1.6-hexane diol di(meth) acrylate, 2-butyl-2-ethyl- 1.3-propane diol di(meth) acrylate, 1.9-decane diol di(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate Ester, EO or PO modified bisphenol A di(meth) acrylate compound, hydroxypyrophosphate neopentyl glycol di(meth) acrylate, 2-hydroxy-3-propenyl methoxy propyl methacrylate , di(meth)acrylic anhydride, and the like. Each of them may be used alone or in combination of two or more. Preferably, from the viewpoint of availability, tripropylene glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, 2-hydroxy-3-propenyloxypropyl group Methacrylate, di(meth)acrylic anhydride. The ratio of use of each of the difunctional (meth) acrylate components when two or more kinds are used is not particularly limited.

The above-described olefin-thiol reaction, in the present invention, means an addition reaction of a reactive unsaturated group of a (meth) acrylonitrile-based compound with a thiol group of a thiol compound. The polyfunctional sulfur (meth) acrylate of the present invention does not include a radical copolymer obtained by radical copolymerization of the above component (A) and component (B). In the case of a radical copolymer, the structure of the general formula (1) of the present invention is not included, but a structure in which only the long-chain polymer of the component (B) is bonded to the terminal of the thiol of the component (A). Although the hard coat property is improved, the workability is low.

The polyfunctional sulfur (meth) acrylate resin of the present invention is a terminal (meth) thiol group of the terminal thiol group (-SH) of the component (A) and at least one end of the component (B). The product obtained by the reaction of an ene-thiol has two or more terminal structures represented by the formula (1). The proportion of the component (B) in the polyfunctional sulfur (meth) acrylate resin of the present invention is preferably a difunctional (meth) acrylate compound of the component (B) relative to one (A) component thiol group. It is a ratio of 1 to 3 molecules. By setting the ratio of the component (B) to such a ratio, it is possible to suppress an increase in the unreacted (B) component and to make the hard coat property more excellent and simultaneously lower. The ratio of the reaction between the two ends of the low (B) component and the thiol group is prevented, the molecular weight is prevented from increasing, the high viscosity is avoided, the mutual solubility with an organic solvent or the like is obtained, and gelation is difficult. From the viewpoint of improving both the workability of the cured product and the hard coat layer, the use ratio of the component (B) is preferably 1 to 2 molecules.

The ene-thiol reaction, although highly reactive, can be carried out without a catalyst, but an acid or an amine catalyst is preferably used. Specifically, examples of the acid catalyst include tin compounds such as tin (IV) octoate and dibutyltin dilaurate; and examples of the amine catalyst include triethylamine, imidazole pyridine, valine acid, and cinchona alkaloid. , triterpene terpene terpene, dioxodicycloundecene, hexahydromethylpyrimidopyridine, dioxodicyclodecane, tetramethylguanidine, dinonbicyclooctane, diisopropylethylamine, tetramethyl Piperidine. These may be used alone or in combination of two or more. Further, the amount of the catalyst to be used is preferably about 0.001 to 0.01 parts by weight based on 100 parts by weight of the total polymerization component.

Further, in the above-mentioned ene-thiol reaction, a polymerization inhibitor such as methoxyphenol, hydroquinone, trimethylhydroquinone or N-nitrosophenylhydroxylamine can be used. The amount of the polymerization inhibitor to be used is not particularly limited, and it is preferably such that it does not adversely affect the reaction hardenability of the obtained resin, and is usually about 1 part by weight or less based on 100 parts by weight based on the total weight of the product. Further, in order to suppress polymerization, air or the like may be poured into the reaction system.

The above-mentioned ene-thiol reaction can obtain a product without a solvent without using an organic solvent. Further, it is also possible to use an organic solvent capable of dissolving each component and synthesizing it in a solvent. In this case, it is advantageous in that the product can be obtained at a low viscosity by the dilution effect of the organic solvent. As a suitable organic solvent, as long as it is a ketone other than, for example, methyl ethyl ketone or methyl isobutyl ketone The external organic solvent is not particularly limited, and those which are conventionally used can be used. When a ketone is used, the reaction of the thiol group of the component (A) with the (meth) acryloyl group of the (B) component is inhibited. Specific examples of the organic solvent include alcohols such as propanol and butanol; aromatic hydrocarbons such as toluene and benzene; butyl acetate and ethyl acetate; and the like may be used alone or in combination. Two or more types are used. In each reaction step, if the reaction temperature is set to a high temperature, the reaction can be carried out with high efficiency and for a short period of time. Therefore, it is preferable to have a high boiling point, but it is preferable that the active energy ray-hardening type hard coat agent should have good drying property. Ethyl acetate, butyl acetate and toluene are preferred.

The present invention is further a polyether sulfur (meth) acrylate resin containing a thioether bond, which has a terminal structure represented by the following formula (2), which is a thiol of the component (A) The terminal is bonded to a (meth) acrylonitrile-alkenyl-thiol reaction of at least one side of the component (B).

(wherein, X represents a structure other than a terminal thiol group in the polyfunctional thiol compound (A). Each of R ₁ and R ₃ is hydrogen or a methyl group, and R ₂ represents O or -OR ₉ -O-. R ₉ is selected from at least one of the following: a linear or branched alkyl group of C1-20, -(CH ₂ CH ₂ O) _m CH ₂ CH ₂ -, -(CH ₂ CH(CH ₃ ) O) _m CH ₂ CH(CH ₃ )-, -CH ₂ CH ₂ OP=O(OH)OCH ₂ CH ₂ -, -CH ₂ CH(OH)CH ₂ -, and the following formula (1-1)~ (1-3) The structure shown. m, p, and q represent positive integers and p+q=2~6.)

The polyfunctional sulfur (meth) acrylate resin of the present invention has a terminal structure in 2 to 6 brackets in one molecule as shown in the formula (2). If there is only one structure shown in the brackets, the hard coat property of the cured film is low. If the structure shown in the brackets is 2 to 6, the hard coat property is improved due to the construction of the dense three-dimensional crosslinked structure. If more than six structures are shown in the parentheses, the control of the ene-thiol reaction becomes difficult and gelatinization is easy.

The ratio of (A) component and (B) component in the polyfunctional sulfur (meth) acrylate resin of the present invention, and the like, and the production method are as described above.

An active energy ray-curable hard coat resin comprising the above polyfunctional sulfur (meth) acrylate resin, a polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups, and a photopolymerization initiator The object is also a ring of the invention. Since the cured product of the active energy ray-curable hard coat resin composition of the present invention has high crosslinking density, it is excellent in hard coat property and excellent in flexibility. Therefore, both the hard coat property and the flexibility of the cured film can be achieved, which is difficult to be developed by adjusting the crosslink density and mixing the unreacted resin, and thus can be suitably used for the decorative hard coat. A component for a film.

The polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups as long as it is a (meth) acrylate having three or more (meth) acrylonitrile groups in one molecule, and It is not particularly limited, and specific examples thereof include trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tris(meth)acrylate, and glycerol ethoxy tris(meth)acrylic acid. Ester, glycerol propoxy tri(meth) acrylate, ethoxylated tris(meth) acrylate, ε-caprolactone denatured tris-(2-(methyl) propylene oxime Oxyethyl)trimeric isocyanate, pentaerythritol tri/tetra(meth)acrylate, pentaerythritol ethoxy tris/tetra(meth)acrylate, pentaerythritol propoxy three/four ( Methyl) acrylate, ditrimethylolpropane tetra(meth) acrylate, dipentaerythritol hexa(meth) acrylate, ε-caprolactone denatured dipentaerythritol hexa(meth) acrylate Ester, urethane (meth) acrylate, polyester (meth) acrylate. These may be used alone or in combination of two or more. Suitable from the viewpoints of hard coatability and hardenability, neopentyl alcohol tri/tetra(meth)acrylate, dipentaerythritol hexa(meth) acrylate, glycerol propoxy three (a) Acrylate, ε-caprolactone denatured tris-(2-(methyl) propylene oxyethyl) trimeric isocyanate, urethane (meth) acrylate, polyester (meth) acrylate. Preferred are urethane (meth) acrylate, neopentyl alcohol tri/tetra (meth) acrylate), and polyester (meth) acrylate. When two or more types are used, the ratio of use of each polyfunctional (meth) acrylate component is not particularly limited.

Examples of the urethane (meth) acrylate include a terminal isocyanate group-containing compound obtained by reacting a polyvalent isocyanate compound with a compound having two or more hydroxyl groups, and a hydroxyl group-containing (meth) acrylate. There are three or more (meth) acrylonitrile groups in the molecule obtained by the reaction. a urethane (meth) acrylate; and a urethane having at least three (meth) acrylonitrile groups in a molecule obtained by reacting a polyvalent isocyanate compound with a hydroxyl group-containing (meth) acrylate compound Ester (meth) acrylate and the like.

The polyester (meth) acrylate is an epoxy group having three or more (meth) acrylonitrile groups obtained by reacting a compound having three or more epoxy groups in a molecule with (meth)acrylic acid. (Meth) acrylate, etc.

The photopolymerization initiator is not particularly limited as long as it can be decomposed by ultraviolet rays and generates radicals, and a conventional one can be used. Specifically, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propyl 1-ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4- (methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide, 4-methyldi Phenyl ketone or the like can be easily obtained from BASF Corporation or the like. These may be used alone or in combination of two or more. The amount of the photopolymerization initiator to be used is preferably from about 0.1 to 10 parts by weight based on 100 parts by weight of the active energy ray-curable resin composition.

The active energy ray-hardening type hard coat resin composition of the present invention can also be mixed with an inorganic filler for the purpose of improving wear resistance or improving barrier properties. As the inorganic filler, a conventional substance such as cerium oxide or metal oxide fine particles can be used without limitation. For example, titanium oxide, aluminum oxide, cerium oxide, tin oxide, zirconium oxide, zinc oxide, cerium oxide, indium oxide, or the like can be given. These may be used alone or in combination of two or more. Among them, Since it is easy and inexpensive to obtain a commercial product group, it is preferable to use cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide.

The average particle diameter of the above inorganic filler is preferably controlled to be 200 nm (by laser diffraction ‧ scattering method). When the average particle diameter exceeds 200 nm, the cured film is likely to be whitened to impair optical characteristics such as haze and transmittance.

The active energy ray-curable hard coat resin composition of the present invention may further be further mixed with an additive as needed. Examples of the above additives include an antioxidant, an ultraviolet absorber, a photostabilizer, an antifoaming agent, a surface conditioner, an antifouling agent, a pigment, an antistatic agent, and a metal oxide fine particle dispersion.

Moreover, the cured film obtained by irradiating the active energy ray-curable hard coat agent with an active energy ray to cure it is also one of the inventions. When the cured film of the present invention is used, a decorative hard coat film which is both workability and hard coatability can be used.

Examples of the active energy ray include light (light such as ultraviolet light), electron beam, X-ray, α-ray, β-ray, γ-ray, neutron beam, and the like. In view of general popularization, it is preferable to use light and electron beams.

The above-mentioned plastic film laminated with a cured film is also one of the inventions. It is possible to impart a hard coating property which is hard to be damaged on the surface of the molded article with respect to the severe surface processing or deep drawing which has not been applied to the crack of the hard coat layer. Specifically, it can be suitably used in an IML method or a film-fitting decoration.

There is no particular limitation on the substrate of the above plastic film. For example, plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, cellulose triacetate resin, ABS resin, AS resin, norbornene) Resin, etc.).

The method for laminating the cured film of the plastic film is carried out by a conventional method in which an active energy ray-curable hard coat resin composition is applied and dried, and then irradiated with an active energy ray to be cured. . Examples of the coating method of the resin composition include a bar coating method, a bar coating method, an air knife coating method, a gravure coating method, a reverse gravure coating method, a lithography method, and a flexographic printing method. Printing, screen printing, etc. Further, the coating amount is not particularly limited, but usually the weight after drying is from 0.1 to 20 g/m ² , preferably from 0.5 to 10 g/m ² .

The present invention is also a plastic injection molded article using the above plastic film. In the past, due to the cracking problem of the hard coat layer, the hard coat property of the plastic injection molded article has to be compromised, or the design is limited. For example, if the plastic film of the present invention is used, the complex design can be obtained. The plastic injection molded article, which is not easily damaged on the surface, can be used in the frame of an electric machine such as a mobile phone terminal or a personal computer, or a part of the interior of the car or the outer cover.

The present invention further laminates the processed article of the above plastic film. The laminating method of the plastic film is different from the method of inserting and molding in the mold and attaching to the plastic molded product, and is to laminate the plastic film on the surface of the plastic processed product formed by injection molding or extrusion molding of the thermoplastic resin. . Moreover, as a processed product, a frame of an electric machine such as a mobile phone terminal or a personal computer, or a part of the interior of the car or the outer cover, and a plastic container can be used. Device.

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited by the examples. In addition, in each case, "part" and "%" are weight basis unless otherwise specified.

<Synthesis Example 1>

In a four-necked flask equipped with a stirrer, a thermometer, a circulation cooler, a nitrogen gas inlet, and a dropping funnel, 31.0 parts of toluene and dimethylol tricyclodecane diacrylate as a component (B) were placed (hereinafter, DCP-A) 31.0 parts, 0.01 parts of triethylamine (hereinafter TEA), 0.2 parts of methoxyphenol, and stirred while heating to 60 ° C, and prepared as a component (A) of tetraethylene glycol double (3) - mercaptopropionate) (hereinafter, EG-MP, corresponding to the above formula (3); x = 186 calculated in formula 1) 19.0 parts, 19.0 parts of toluene mixed solution, all from the dropping funnel took 2 hours into the mixture . Thereafter, the mixture was kept at 60 ° C for 5 hours to obtain a thioether-bonded difunctional acrylate (resin 1) having a terminal structure of the formula (1).

<Synthesis Example 2>

In a four-necked flask equipped with a stirrer, a thermometer, a circulation cooler, a nitrogen gas inlet, and a dropping funnel, 30.8 parts of butyl acetate was added as a component (B) of 2-hydroxy-3-propenyloxypropyl group. 30.8 parts of methacrylate (trade name "NK ester 701A" Xinzhongcun Chemical Industry Co., Ltd.), 0.01 parts of TEA, and 0.2 parts of methoxyphenol were stirred and heated to 60 ° C, and prepared as (A) in advance. Trimethylolpropane tris(3-mercaptopropionate) (hereinafter, TM-MP, corresponding to the above formula (4); x = 133) 19.2 parts mixed solution with butyl acetate 19.2 parts The whole amount was dripped from the dropping funnel for 2 hours. Thereafter, the mixture was kept at 60 ° C for 5 hours to obtain a triether methacrylate (resin 2) containing a thioether bond having a terminal structure of the formula (1).

<Synthesis Example 3>

In a four-necked flask equipped with a stirrer, a thermometer, a circulation cooler, a nitrogen gas inlet, and a dropping funnel, 31.9 parts of butyl acetate was added as a component (B) of tetraethylene glycol diacrylate (hereinafter, 4EGA) 31.9 parts, 0.01 parts of TEA, 0.2 parts of methoxyphenol and stirred while heating to 60 ° C, and prepared as a component (A), tris-[(3-mercaptopropoxy)-ethyl]-three A mixed solution of polyisocyanate (hereinafter, TI-MP, corresponding to the above formula (5); x = 176) of 18.1 parts and butyl acetate (18.1 parts) was added dropwise from the dropping funnel for 2 hours. Thereafter, the mixture was kept at 60 ° C for 5 hours to obtain a trifunctional acrylate (resin 3) containing a thioether bond, and the thioether bond had a terminal structure of the formula (1).

<Synthesis Example 4>

In a four-necked flask equipped with a stirrer, a thermometer, a circulation cooler, a nitrogen gas inlet, and a dropping funnel, 39.8 parts of toluene, 3,400 parts of tripropylene glycol diacrylate (hereinafter, TPGDA) as a component (B), and TEA0 were charged. .01 parts, 0.2 parts of methoxyphenol and stirred, while heating to 60 ° C, the pre-prepared as the (A) component of pentaerythritol-tetrakis(3-mercaptopropionate), PT-MP, corresponding to A mixed solution of 10.7 parts of the above formula (6), x = 123) and 10.7 parts of toluene was added dropwise from the dropping funnel over 2 hours. Thereafter, the mixture was kept at 60 ° C for 5 hours to obtain a thioether-bonded tetrafunctional acrylate (resin 4) having a terminal structure of the formula (1).

<Synthesis Example 5>

In a four-necked flask equipped with a stirrer, a thermometer, a circulation cooler, a nitrogen inlet, and a dropping funnel, 35.6 parts of butyl acetate, 35.6 parts of NK ester 701A as component (B), 0.01 parts of TEA, and A were charged. 0.2 parts of oxyphenol and stirred while heating to 60 ° C, pre-prepared as neopreneol-hexa(3-mercaptopropionate) as component (A) (hereinafter, DP-MP, corresponding to the above formula (7); x = 131) A mixed solution of 14.4 parts of butyl acetate and 14.4 parts of butyl acetate was added dropwise from the dropping funnel for 2 hours. Thereafter, the mixture was kept at 60 ° C for 5 hours to obtain a thioether-bonded hexafunctional methacrylate (resin 5) having a terminal structure of the formula (1).

<Example 1>

100 parts of the thioether-bonded difunctional propylene obtained in Synthesis Example 1 The acid ester (resin 1) was mixed with 50 parts of pentaerythritol triacrylate (hereinafter, PE3A), 5 parts of a photopolymerization initiator (trade name "Irgaqure 184" BASF), and 95 parts of methyl ethyl ketone (hereinafter, MEK). An active energy ray-curable hard coat resin composition having a solid content of 40% was prepared.

<Example 2>

100 parts of the triether methacrylate (resin 2) containing the thioether bond obtained in Synthesis Example 2, 116.7 parts of PE3A, 8.3 parts of Irgaqure 184, and 191.7 parts of MEK were mixed to form 40% active energy line hardening. Type hard coating resin composition.

<Example 3>

For 100 parts of the thioether-bonded trifunctional methacrylate (resin 2) obtained in Synthesis Example 2, a 6-functional urethane acrylate (trade name "UA-306H"; Kyoeisha Chemical Co., Ltd.) was mixed. 50 parts, Irgaqure 184® 5 parts, MEK 95 parts, made of a 40% active energy line hardening type hard coat resin composition.

<Example 4>

In a four-necked flask equipped with a stirrer, a thermometer, a circulation cooler, a nitrogen inlet, and a dropping funnel, 39.5 parts of methyl isobutyl ketone was charged, and the temperature was raised to 110 ° C under a nitrogen stream, and then the propylene was charged. A dropping funnel of a mixture of 26.0 parts of methacrylic acid ester (hereinafter, GMA) and 1.2 parts of azobisisobutyronitrile was added dropwise in a total amount of 2 hours, and the reaction was carried out for 5 hours to obtain a GMA copolymer. Thereafter, after cooling to room temperature, 13.2 parts of acrylic acid, 0.3 parts of triphenylphosphine, and 0.1 part of methoxyphenol were charged, and the dropping funnel was removed, and the nitrogen inlet was replaced with an air pumping device while stirring the air while stirring. °C reaction 6 small At this time, a polyester acrylate having a weight average molecular weight of 17,000 was obtained. 125 parts of the polyester acrylate of 125 parts, 100 parts of the triether methacrylate (resin 2) containing the thioether bond obtained in Synthesis Example 2, 5 parts of Irgaqure 184®, and 20 parts of MEK were mixed to form a solid component. 40% active energy ray hardening type hard coat resin composition.

<Example 5>

For 100 parts of the thioether-bonded trifunctional acrylate (Resin 3) obtained in Synthesis Example 3, 116.7 parts of PE3A, 8.3 parts of Irgaqure 184®, and 191.7 parts of MEK were mixed to form 40% active energy line hardening. Type hard coating resin composition.

<Example 6>

For 100 parts of the thioether-bonded tetrafunctional acrylate (Resin 4) obtained in Synthesis Example 4, 50 parts of glycerin triacrylate (trade name "DENACOL DA-314"; Changchun Chemical Industry Co., Ltd.) was mixed. , Irgaqure 184® 5 parts, MEK 95 parts, made into solid ingredients 40% Active energy ray hardening type hard coat resin composition.

<Example 7>

100 parts of the thioether-bonded hexafunctional methacrylate (resin 5) obtained in Synthesis Example 5, mixed with ε-caprolactone denatured tris-(2-(methyl) propylene oxiranyl) three Polyisocyanate (trade name "NK ester A-9300-1CL"; Xinzhongcun Chemical Industry Co., Ltd.) 50 parts, Irgaqure 184® 5 parts, MEK 95 parts, made up of 40% active energy line hardening type hard coating resin Things.

<Comparative Example 1>

Using pentaerythritol three, which is generally known as a hard coating agent constituent Acrylate is used as a comparison. 100 parts of the commercial product "ARONIX M305" (manufactured by Toagosei Co., Ltd.) was mixed with Irgaqure 184® 5.0 parts and MEK 145 parts, and the mixture was made into a 40% solid hard coating agent as a comparative example. .

<Comparative Example 2>

For the purpose of providing flexibility by lowering the crosslinking density, a part of the resin composition of Comparative Example 1 was replaced with a monofunctional acryl oxime monomer: isodecyl acrylate. 75.0 parts of ARONIX M305, 25.0 parts of isodecyl acrylate, 5.0 parts of Irgaqure 184®, and 145 parts of MEK were mixed to prepare a 40% active energy ray resin composition.

<Comparative Example 3>

An unreacted resin having no radical polymerizable group was mixed with the resin composition of Comparative Example 1 for the purpose of providing flexibility. 80 parts of ARONIX M305, saturated polyester resin - 33.3 parts of "KA-2056" (Arakawa Chemical Industry Co., Ltd.), 5 parts of Irgaqure 184®, and 131.7 parts of MEK were mixed to prepare a 40% active energy ray resin composition.

<Comparative Example 4>

100 parts of UA-306H, 5 parts of Irgaqure 184®, and 145 parts of MEK were mixed to prepare a 40% active energy ray resin composition.

<Comparative Example 5>

100 parts of DENACOL DA-314, 5 parts of Irgaqure 184®, and 145 parts of MEK were mixed to prepare a 40% active energy ray resin composition.

<Comparative Example 6>

Equipped with a mixer, thermometer, circulating cooler, nitrogen inlet 39.5 parts of methyl isobutyl ketone was placed in the four-necked flask of the dropping funnel, and the temperature was raised to 110 ° C under a nitrogen stream, and then 26.0 parts of glycidyl methacrylate (hereinafter, GMA) was charged, and A dropping funnel of a mixture of 1.2 parts of azobisisobutyronitrile was added dropwise in a total amount of 2 hours, and reacted for 5 hours to obtain a GMA copolymer. Thereafter, after cooling to room temperature, 13.2 parts of acrylic acid, 0.3 parts of triphenylphosphine, and 0.1 part of methoxyphenol were charged, and the dropping funnel was removed, and the nitrogen gas inlet was replaced with an air pumping device while stirring air at 110 ° C. After reacting for 6 hours, a polyester acrylate having a weight average molecular weight of 17,000 was obtained. To 100 parts of the polyester acrylate, 2 parts of Irgaqure 184® was mixed to prepare a 40% active energy ray-curable hard coat resin composition.

<Comparative Example 7>

100 parts of NK ester A-9300-1CL, 5 parts of Irgaqure 184®, and 145 parts of MEK were mixed to prepare a 40% active energy ray resin composition.

<Comparative Example 8>

100 parts of ε-caprolactone modified as a flexible polyfunctional acrylate, dipentaerythritol hexaacrylate, trade name "DPCA-120" (Nippon Chemical Co., Ltd.), and Irgaqure 184® 5 parts, MEK 145 parts were mixed and made into a 40% active energy ray resin composition.

<Comparative Example 9>

In a four-necked flask equipped with a stirrer, a thermometer, a circulation cooler, and a nitrogen inlet, 15.9 parts of isophorone diisocyanate and polycarbonate diol (quantitative average molecular weight of 1000, trade name "Duranol T6001" Asahi Kasei Chemicals 35.8 parts, 40 parts of methyl isobutyl ketone, heated to 60 ° C while stirring, and kept for 1 hour, then added 0.05 parts of dibutyltin diacetate, at 80 . After reacting at ° C for 2 hours, isophorone diisocyanate was added to both ends of the OH group of the polycarbonate diol, and an isocyanate group was introduced at both ends of the polycarbonate. Thereafter, the mixture was cooled to 40 ° C, and charged with 8.3 parts of 2-hydroxyethyl acrylate and 0.05 part of dibutyltin diacetate, and heated to 80 ° C for 5 hours to form 2-hydroxyethyl acrylate at the end of the isocyanate. OH group, polycarbonate urethane diacrylate (resin 6) was obtained. After cooling to room temperature, 5 parts of Irgaqure 184® and 47 parts of MEK were mixed to prepare a 40% active energy ray resin composition.

The hard coating agent of each of the examples and the comparative examples was applied to a sheet having a thickness of 188 μm by a No. 12 bar coater to easily treat a polyethylene terephthalate film (trade name "COSMOSHINE A4100" Toyobo Co., Ltd. The easy-adhesive surface of the company was dried at 80 ° C for 1 minute, and then irradiated with ultraviolet rays of 300 mJ/cm ² to obtain a cured film having a film thickness of 5 μm.

The cured film formed using the hard coating agents of the respective examples and comparative examples was evaluated as a hard coat property by a pencil hardness test and a scratch resistance test. The evaluation of the workability was evaluated by elongation and flexibility, which was obtained by a tensile test in which the cured film was extended in one direction. The evaluation results of these are shown in Table 3.

(pencil hardness test)

The pencil hardness was evaluated in accordance with JIS-K-5600. When the pencil hardness F or more is regarded as excellent hardness and it is evaluated as satisfying the hard coat property, the pencil hardness B or less is evaluated as poor hard coat property.

(Evaluation of scratch resistance)

Using #0000 steel wool, load 100 g/cm ² load, and repeatedly scratch the surface of the cured film 10 times, and visually confirm whether there was a flaw. The evaluation results were as follows: if there is no scratch, it is evaluated as having excellent hard coat properties, and if it is a plurality of scratches, it can be used as a hard coater, and many flaws are not suitable as a hard coater.

(extension)

The elongation is a strip test piece in which the cured film is cut into a length of 100 mm and a width of 7 mm, and the test piece is placed on a tensile tester (model "RTC-1250A", Orientec) at a distance of 50 mm between the chucks, at room temperature of 25 ° C, In an environment with a humidity of 45% RH, the tensile speed is 10 mm/min, and the distance between the chucks is changed to 60 mm (extension 20%), 65 mm (extension 30%), and 70 mm (extension 40%). Stop and visually observe whether the hardened film has cracks. The crack is evaluated as ○; the crack is evaluated as ×. The softness of the cured film can be evaluated by measuring the elongation of the cured film. When the elongation is large, the soft cured film is, for example, softly conformed to the stress of stretching in the molding process of the coated film, so that the crack of the cured film can be reduced, and workability can be imparted.

(evaluation of flexibility)

The surface of the cured film was rolled outwardly into a cylinder of φ 2 mm to visually confirm the presence of cracks. If there is no crack, it is ○, and if there is crack, it is ×.

Claims (8)

A polyfunctional sulfur (meth) acrylate resin characterized by having two or more terminal structures represented by the general formula (1), which is a thiol terminal of a polyfunctional thiol compound (A), and a bifunctional (A) The (meth)acryloyl group having at least one terminal of the acrylate compound (B) is subjected to an ene-thiol reaction, and the polyfunctional thiol compound (A) is calculated by the formula 1 and the x is 100. Above and 200 or less, wherein the polyfunctional thiol compound (A) does not contain a polyfunctional thiol compound represented by the following general formula (6): (wherein, X represents a structure other than a terminal thiol group in the polyfunctional thiol compound (A); R ₁ and R ₃ each represent hydrogen or a methyl group; and R ₂ represents O or -OR ₉ -O-; R ₉ is selected from at least one of the following: a linear or branched alkyl group of C1-20, -(CH ₃ CH ₂ O) _m CH ₂ CH ₂ -, -(CH ₂ CH(CH _{3 )} O) _m CH ₂ CH(CH ₃ )-, -CH ₂ CH ₂ OP=O(OH)OCH ₂ CH ₂ -, -CH ₂ CH(OH)CH ₂ - and the following formula (1-1)~ (1-3) The structure shown; m, p, and q represent positive integers, and p+q=2~6) (wherein R ₇ represents hydrogen or methyl). A polyfunctional sulfur (meth) acrylate resin having a terminal structure represented by the general formula (2), which is a thiol terminal of a polyfunctional thiol compound (A), and a difunctional (meth) acrylate compound (B) The (meth)acryloyl group having at least one terminal is bonded by an ene-thiol reaction, and the polyfunctional thiol compound (A) is calculated by the formula 1 and x is 100 or more and 200 or less. Wherein the polyfunctional thiol compound (A) does not comprise a polyfunctional thiol compound represented by the following general formula (6): (wherein, X represents a structure other than a terminal thiol group in the polyfunctional thiol compound (A); R ₁ and R ₃ each represent hydrogen or a methyl group, and R ₂ represents O or -OR ₉ -O-; R ₉ is selected from at least one of the following: a linear or branched alkyl group of C1-20, -(CH ₂ CH ₂ O) _m CH ₂ CH ₂ -, -(CH ₂ CH(CH ₃ ) O) _m CH ₂ CH(CH ₃ )-, -CH ₂ CH ₂ OP=O(OH)OCH ₂ CH ₂ -, -CH ₂ CH(OH)CH ₂ - and the following formula (1-1)~( 1-3) The structure shown; m, p, and q represent positive integers, and p+q=2~6, n represents an integer from 2 to 6) (wherein R ₇ represents hydrogen or methyl). A polyfunctional sulfur (meth) acrylate resin according to claim 1 or 2, wherein the polyfunctional thiol compound (A) comprises polyfunctional sulphur represented by the following formulas (3) to (5) and (7) Any one or more of the alcohol compounds: (wherein R ₄ represents hydrogen or methyl, and n represents an integer from 1 to 12); (wherein R ₅ represents hydrogen or methyl); [Chemical 5] (wherein R ₆ represents hydrogen or methyl); (wherein R ₈ represents hydrogen or methyl). An active energy ray-curable hard coat resin composition characterized by comprising: a polyfunctional sulfur (meth) acrylate resin according to any one of claims 1 to 3; having three or more (methyl) a polyfunctional (meth) acrylate of acrylonitrile; and a photopolymerization initiator. A cured film obtained by irradiating an active energy ray-hardening resin composition of the fourth aspect of the patent application with an active energy ray to harden it. A plastic film which is laminated with a cured film as in claim 5 of the patent application. A plastic injection molding product which uses a plastic film as claimed in claim 6 of the patent application. A processed product having a plastic film as claimed in claim 6 of the patent application.