JP2013213200A - Multifunction thio(meth)acrylate resin, active energy ray curable hard coat resin composition comprising the same, cured film obtained by curing the same, plastic film having cured film laminated thereon, plastic injection molding using the plastic film, and processed product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multifunction thio(meth)acrylate resin that can form a cured film that has high hardness and scratch resistance, excels in hard coat properties, and that has high flexibility having high elongation and bending properties.SOLUTION: A multifunction thio(meth)acrylate resin is configured such that a thiol terminal of a polyfunctional thiol compound (A) in which (x) calculated by formula X=(Mw of the polyfunctional thiol compound (A))/(the number of thiol groups of the polyfunctional thiol compound (A) in one molecule) is at least 100 and at most 200, and a (meth)acryloyl group which at least one terminal of a bifunctional (meth)acrylate compound (B) has are subjected to ene-thiol reaction, and has two or more terminal structures represented by general formula (1). The multifunction thio(meth)acrylate resin is used.

Description

The present invention relates to a polyfunctional thio (meth) acrylate resin, an active energy ray-curable hard coat resin composition containing the same, a cured film thereof, a plastic film in which the cured film is laminated, and a plastic injection molded product using the plastic film And processed products.

As a manufacturing method to add decoration and scratch resistance to the surface of plastic products, (1) Adhesive layer, pattern layer, and hard coat layer are laminated on plastic film such as PET (polyethylene terephthalate). (2) In-mold molding, in-mold decolating, in-mold laminating, etc., in which a hard coat film for decoration is inserted into a mold and attached to a plastic molded product at the same time as injection molding) Attention has been focused on a film bonding decoration method in which an injection-molded plastic product surface, a steel plate, and a building material are bonded with a decorative hard coat film.

In the above construction method, the decorative hard coat film is stretched along the inner surface of the mold or the product shape of the molded product. However, since the hard coat properties generally become harder and more brittle, the decorative hard coat film used in the above construction method is prone to cracking due to stress during stretching, and the workability is reduced. . Specifically, cracks are likely to occur in curved surface processing or box-shaped processing (called deep drawing), and instead of reducing hard coat properties, flexibility is given to improve workability, or design. Was limited.

In recent years, in order to differentiate products, there has been a demand for complicated design and difficulty in scratching the surface, and it is indispensable to achieve both flexibility and hard coat properties in a hard coat film. Various methods have been proposed for this. For example, the method of controlling the crosslinking density by the composition of trifunctional or higher (meth) acrylic oligomer and mono- or bifunctional (meth) acrylic monomer can be mentioned (see Patent Document 1). According to this method, a hard coat film with high surface hardness and flexibility that can follow deformation during molding can be obtained, but the surface hardness and flexibility are in a trade-off relationship, and a compromise is achieved with a certain balance. There was a problem that it had to be done.

As another example, a polymer (meth) acrylate having a molecular weight of 5,000 to 50,000 (meth) acryloyl equivalent of 200 g / eq or more and 800 g / eq or less, and a (meth) acrylate having a molecular weight of 1,000 to 10,000 (meta ) A method of blending a polyfunctional urethane (meth) acrylate having an acryloyl equivalent of 100 g / eq or more and less than 200 g / eq has been proposed (see Patent Document 2). However, this also defines the balance between the tradeoff between hard coat properties and flexibility in terms of (meth) acryloyl equivalent, and must be compromised with a certain balance.

Furthermore, a method of imparting processability by blending a non-reactive resin having no radical polymerizable double bond with a (meth) acrylic monomer has been proposed (see Patent Document 3). However, when such a non-reactive resin or plastic resin is blended, it becomes flexible and processability is improved, but it has been difficult to achieve high hard coat properties that have been required in recent years.

JP 2011-148964 A JP 2004-123780 A JP 2008-208154 A

An object of the present invention is to provide a polyfunctional thio (meth) acrylate resin that has a hard coat property and is capable of forming a cured film having high flexibility and excellent workability.

That is, the present invention 1 includes a thiol terminal of a polyfunctional thiol compound (A) (hereinafter also referred to as (A) component) in which x calculated by Formula 1 is 100 to 200, and a bifunctional (meth) acrylate compound A (meth) acryloyl group having at least one terminal of (B) (hereinafter also referred to as component (B)) is formed by an ene-thiol reaction and has two or more terminal structures represented by the general formula (1). It is a functional thio (meth) acrylate resin.
(In the formula, X represents a structure excluding the terminal thiol group of the polyfunctional thiol compound (A). R ₁ and R ₃ are each hydrogen or a methyl group, R ₂ is O, or —O—R ₉ —O—. R ₉ represents a C1-20 linear or branched alkylene group, — (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 general formula (1-1) to (1-3 ) M, p and q are positive integers and p + q = 2-6.)

In addition, the present invention 2 is represented by the following general formula (2) in which the thiol terminal of the component (A) and the (meth) acryloyl group possessed by at least one terminal of the component (B) are bonded by an ene-thiol reaction. It is a polyfunctional thio (meth) acrylate resin having a terminal structure.
(In the formula, X represents a structure excluding the terminal thiol group of the polyfunctional thiol compound (A). R ₁ and R ₃ are each hydrogen or a methyl group, R ₂ is O, or —O—R ₉ —O—. R ₉ represents a C1-20 linear or branched alkylene group, — (CH ₂ CH ₂ O) _m CH ₂ CH ₂ —, — (CH ₂ CH (CH ₃ ) O) _m CH _2. CH (CH ₃ ) — and —CH ₂ CH ₂ OP═O (OH) OCH ₂ CH ₂ —, —CH ₂ CH (OH) CH ₂ —, and the following general formulas (1-1) to (1) -3) is at least one selected from the structure represented by m), p, q are positive integers, and p + q = 2-6.

Moreover, this invention 3 is polyfunctional thio (meth) acrylate resin whose (A) component is any of the polyfunctional thiol compounds represented by the following general formula (3)-(7) in this invention 1 or 2. is there.
(In the formula, R ₄ represents hydrogen or a methyl group, and n represents an integer of 1 to 12.)
(In the formula, R ₅ represents hydrogen or a methyl group.)
(In the formula, R ₆ represents hydrogen or a methyl group.)
(In the formula, R ₇ represents hydrogen or a methyl group.)
(In the formula, R ₈ represents hydrogen or a methyl group.)

Moreover, this invention 4 is active energy containing the polyfunctional thio (meth) acrylate resin in any one of this invention 1-3, the polyfunctional (meth) acrylate which has 3 or more of (meth) acryloyl groups, and a photoinitiator. It is a line curable hard coat resin composition.

Moreover, this invention 5 is a cured film obtained by making the active energy ray hardening-type hard coat resin composition of this invention 4 harden | cure by irradiating with an active energy ray.

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

The present invention 7 is a plastic injection molded product using the plastic film of the present invention 6.

Moreover, this invention 8 is a processed product which laminated | stacked the plastic film of this invention 6. FIG.

Use of the thioether bond-containing polyfunctional thio (meth) acrylate resin of the present invention achieves both flexibility and excellent hard coat properties (excellent surface scratch resistance) having high pencil hardness and scratch resistance. A cured film can be formed. Thereby, it is possible to form a hard coat film that not only has high workability, which is difficult with the prior art, but also can impart the difficulty of scratching the surface of the cured film.

The component (A) in the present invention is not particularly limited as long as it is not a monofunctional thiol compound but a polyfunctional thiol compound having two or more thiol groups (—SH) at the ends as reactive functional groups. By making the component (A) a polyfunctional thiol compound, the resin of the present invention can be a polyfunctional thio (meth) acrylate resin having two or more (meth) acryloyl groups at the terminal, and active energy rays. The cured product obtained by irradiating can easily have a dense three-dimensional crosslinked structure, and thus can have excellent hard coat properties. The polyfunctional thio (meth) acrylate resin in the present specification means a polyfunctional (meth) acrylate containing two or more thioether bonds.

Further, the component (A) may have a polyfunctional thio (meth) acrylate resin that forms a cured film having hard coat properties in which x calculated from Formula 1 is 100 to 200. This is preferable. When x is 100 to 200, a dense three-dimensional crosslinked structure can be obtained and more excellent hard coat properties can be imparted. Specific examples include tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercapto) represented by general formulas (3) to (7). And polyfunctional thiol compounds such as propionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol hexakis (3-mercaptopropionate), and the like. A mixture of seeds or more can be used. From the viewpoint of availability, polyfunctional thiol compounds represented by general formulas (3) to (7) are more preferable.

The component (B) is not particularly limited as long as it is a bifunctional (meth) acrylate having a (meth) acryloyl group at at least one terminal. When a trifunctional or higher polyfunctional (meth) acrylate compound is used, a cross-linking structure between molecules is easily formed by an ene-thiol reaction with the polyfunctional thiol compound, resulting in gelation. It tends to occur and reaction control becomes difficult. Specific examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 3-methyl-1.5-pentanediol di (meth) acrylate, 1.6-hexanediol di (meth) acrylate 2-butyl-2-ethyl-1.3-propanediol di (meth) acrylate, 1.9-nonanediol di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, EO or PO-modified bisphenol A Examples include di (meth) acrylate compounds, hydroxypivalic acid neopentyl glycol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and di (meth) acrylic anhydride. These may be used alone or in combination of two or more. More preferably, in terms of easy availability, tripropylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, di (meth) acrylic anhydride It is a thing. The ratio of each bifunctional (meth) acrylate component used when two or more are used is not particularly limited.

In the present invention, the ene-thiol reaction refers to an addition reaction between a reactive unsaturated group of a (meth) acryloyl compound and a thiol group of a thiol compound. The polyfunctional thio (meth) acrylate of the present invention does not include a radical copolymer resulting from the radical copolymerization reaction of the component (A) and the component (B). When the radical copolymer is used, the structure of the general formula (1) of the present invention is not included, and a long-chain polymer composed only of the component (B) is bonded to the thiol terminal of the component (A), and the hard coat property is Although improved, the processability tends to decrease.

In the polyfunctional thio (meth) acrylate resin of the present invention, the terminal thiol group (-SH) of the component (A) and the (meth) acryloyl group having at least one terminal of the component (B) are ene-thiol reaction. The product thus obtained has two or more terminal structures represented by the general formula (1). The use ratio of the component (B) in the polyfunctional thio (meth) acrylate resin of the present invention is 1 to 3 molecules of the bifunctional (meth) acrylate compound of the component (B) with respect to one thiol group of the component (A). The ratio is preferably By setting the ratio of the component (B) to this ratio, an increase in the unreacted component (B) can be suppressed, the hard coat property can be further improved, and both ends of the component (B) The probability of reacting with the thiol group is lowered, the increase in molecular weight is prevented, the increase in viscosity is prevented, the compound has good compatibility with an organic solvent and the like, and further, it is difficult to gel. More preferably, the use ratio of the component (B) is 1 to 2 molecules from the viewpoint that both the workability of the cured product and the hard coat property are excellent.

Although the ene-thiol reaction is highly reactive and proceeds even without a catalyst, it is preferable to use an acid or an amine catalyst. Specifically, for example, tin compounds such as stannous octylate and dibutyltin dilaurate as the acid catalyst, and triethylamine, imidazolidine, proline, quinaalkaloid, triazabicyclodecene, diazabicyclo as the amine catalyst, for example. Examples include undecene, hexahydromethylpyrimidopyridine, diazabicyclononane, tetramethylguanidine, diazabicyclooctane, diisopropylethylamine, and tetramethylpiperidine. These may be used alone or in combination of two or more. In addition, it is preferable that the usage-amount of the said catalyst shall be about 0.001-0.01 weight part with respect to 100 weight part of all the polymerization components.

In the ene-thiol reaction, a polymerization inhibitor such as methoquinone, hydroquinone, trimethylhydroquinone, N-nitrosophenylhydroxylamine can be used. The amount of the polymerization inhibitor used is not particularly limited, but is usually about 1 part by weight or less with respect to 100 parts by weight of the total product weight so as not to adversely affect the reaction curability of the resulting resin. It is preferable to do. In order to prevent polymerization, air may be blown into the reaction system.

In the ene-thiol reaction, a product can be obtained without using an organic solvent without using a solvent. Moreover, the synthesis | combination in a solvent is also possible using the organic solvent which can melt | dissolve each component, In that case, there exists a merit which can obtain a product with low viscosity by the dilution effect of an organic solvent. As a preferable organic solvent, any known organic solvent can be used without particular limitation as long as it is an organic solvent other than ketones such as methyl ethyl ketone and methyl isobutyl ketone. When ketones are used, the ene-thiol reaction between the thiol group of the component (A) and the (meth) acryloyl group of the component (B) is inhibited. Specific examples of suitable organic solvents include alcohols such as propanol and butanol; aromatic hydrocarbons such as toluene and benzene; butyl acetate and ethyl acetate. These may be used alone. Two or more kinds may be mixed and used. In each reaction step, if the reaction temperature is set high, the reaction can proceed efficiently and in a short time. Therefore, a high boiling point is preferable, but an active energy ray-curable hard coat agent preferably has good drying properties. Considering the point, ethyl acetate, butyl acetate, and toluene are preferable.

The present invention also provides a thioether bond having a terminal structure represented by the following general formula (2) in which the thiol terminal of the component (A) and at least one (meth) acryloyl group of the component (B) are bonded by an ene-thiol reaction. It is also a polyfunctional thio (meth) acrylate resin containing.
(In the formula, X represents a structure excluding the terminal thiol group of the polyfunctional thiol compound (A). R ₁ and R ₃ are each hydrogen or a methyl group, R ₂ is O, or —O—R ₉ —O—. R ₉ represents a C1-20 linear or branched alkylene group, — (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 general formula (1-1) to (1-3 ) M, p and q are positive integers and p + q = 2-6.)

The polyfunctional thio (meth) acrylate resin of the present invention has a terminal structure in parentheses of 2 to 6 in one molecule as represented by the general formula (2). If the structure represented in parentheses is only 1, the hard coat property of the cured film is lowered. When the structure represented in parentheses is 2 to 6, the hard coat property is improved because a dense three-dimensional crosslinked structure is constructed. If the structure represented in parentheses exceeds 6, the control of the ene-thiol reaction becomes difficult and gelation tends to occur.

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

An active energy ray-curable hard coat resin composition containing the polyfunctional thio (meth) acrylate resin, a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups, and a photopolymerization initiator is also one aspect of the present invention. One. The cured product of the active energy ray-curable hard coat resin composition of the present invention is excellent in hard coat properties and flexibility because of its high crosslink density. Therefore, it is possible to achieve both hard coat properties and flexibility of the cured film, which has been difficult with methods such as the adjustment of the crosslink density and the formulation of unreacted resin, which have been studied in the past. It can be used suitably for a member.

The polyfunctional (meth) acrylate having three or more (meth) acryloyl groups is not particularly limited as long as it is a (meth) acrylate having three or more (meth) acryloyl group ends in one molecule. Are trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, glycerin ethoxytri (meth) acrylate, glycerin propoxytri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ε-caprolactone Modified tris- (2- (meth) acryloxyethyl) isocyanurate, pentaerythritol tri / tetra (meth) acrylate, pentaerythritol ethoxytri / tetra (meth) acrylate, pentaerythritol propoxytri / tetra Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, .epsilon.-caprolactone-modified dipentaerythritol hexa (meth) acrylate, urethane (meth) acrylates, polyester (meth) acrylate. These may be used alone or in combination of two or more. From the viewpoint of hard coat properties and curability, pentaerythritol tri / tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin propoxytri (meth) acrylate, ε-caprolactone modified tris- (2- (meta ) Acryloxyethyl) isocyanurate, urethane (meth) acrylate, polyester (meth) acrylate. More preferred are urethane (meth) acrylate, pentaerythritol tri / tetra (meth) acrylate, and polyester (meth) acrylate. The usage ratio of each polyfunctional (meth) acrylate component when two or more are used is not particularly limited.

As the urethane (meth) acrylate, in a molecule obtained by reacting a hydroxyl group-containing (meth) acrylate with a terminal isocyanate group-containing compound obtained by reacting a polyvalent isocyanate compound and two or more hydroxyl group-containing compounds. In a molecule obtained by reacting a urethane (meth) acrylate having 3 or more (meth) acryloyl groups and a (meth) acrylate compound containing a polyvalent isocyanate compound and one hydroxyl group, 3 or more (meth) Examples thereof include urethane (meth) acrylate having an acryloyl group.

Examples of the polyester (meth) acrylate include epoxy (meth) acrylate having 3 or more (meth) acryloyl groups obtained by reacting a compound containing 3 or more epoxy groups in the molecule with (meth) acrylic acid. It is done.

The photopolymerization initiator is not particularly limited as long as it can be decomposed by ultraviolet rays to generate radicals to initiate polymerization, and known ones can be used. Specifically, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6- Examples thereof include trimethylbenzoyl-diphenyl-phosphine oxide and 4-methylbenzophenone, which can be easily obtained from BASF. These can be used alone or in combination of two or more. The amount of the photopolymerization initiator used is preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin composition.

The active energy ray-curable hard coat resin composition of the present invention may be blended with an inorganic filler for the purpose of improving wear resistance and blocking property. As the inorganic filler, known ones such as silica and metal oxide fine particles can be used without limitation. Examples thereof include titanium oxide, aluminum oxide, antimony oxide, tin oxide, zirconium oxide, zinc oxide, cerium oxide, and indium oxide. These can be used individually by 1 type or in combination of 2 or more types. Of these, silica, titanium oxide, aluminum oxide, zirconium oxide and zinc oxide are preferred because they are commercially available, easily available, and inexpensive.

It is preferable to use the inorganic filler having an average particle diameter of 200 nm or less (by laser diffraction / scattering method). If the average particle diameter exceeds 200 nm, the cured film is likely to be whitened, and optical properties such as haze and transmission efficiency may be impaired.

The active energy ray-curable hard coat resin composition of the present invention may further contain an additive as necessary. Examples of the additive include antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface conditioners, antifouling agents, pigments, antistatic agents, and metal oxide fine particle dispersions.

Moreover, the cured film obtained by making it harden | cure by irradiating an active energy ray to the said active energy ray hardening-type hard-coat agent is also one of this invention. If the cured film of the present invention is used, it can be used as a decorated hard coat film having both workability and hard coat properties.

Examples of the active energy rays include light (light rays such as ultraviolet rays), electron beams, X-rays, α rays, β rays, γ rays, and neutron rays. Light and electron beams are preferred because they are generally widespread.

A plastic film on which the cured film is laminated is also one aspect of the present invention. It can also be applied to curved surface tight processing and deep drawing processing that could not be adapted from cracks in the hard coat layer so far, and it can impart hard coat properties to the surface of molded products equivalent to conventional ones it can. Specifically, it can be suitably used for the IML method and film bonding decoration.

The substrate of the plastic film is not particularly limited. For example, plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin) Etc.).

As a method of laminating a cured film on the plastic film, it is performed by applying an active energy ray-curable hard coat resin composition and drying it by a known method and then irradiating and curing the active energy ray. Examples of the method for applying the resin composition include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. The coating amount is not particularly limited, but is usually within a range where the weight after drying is 0.1 to 20 g / m ² , preferably 0.5 to 10 g / m ² .

The present invention is also a plastic injection molded product using the plastic film. Conventionally, due to the problem of cracks in the hard coat layer, there was a strong compromise in the hard coat properties of plastic injection molded products, or there was a limitation in design properties. However, if the plastic film of the present invention is used, the design becomes complicated. It is possible to obtain a plastic injection molded product that is compatible and hardly scratches the surface, and can be used for a casing of an electric device such as a mobile phone terminal or a personal computer, a part of an interior trim or exterior cover of a vehicle.

The present invention is also a processed product in which the plastic film is laminated. The plastic film lamination method is different from the method of inserting into a mold and sticking to a plastic molded product at the same time as injection molding, and the plastic film is bonded to the surface of a plastic processed product that is injection-molded or extruded. Is. Moreover, as processed products, it can be used for casings of electrical equipment such as mobile phone terminals and personal computers, interior trims and parts of exterior covers, and plastic containers.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, all parts and% are based on weight unless otherwise specified.

<Synthesis Example 1>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet and dropping funnel, 31.0 parts of toluene, dimethylol tricyclodecane diacrylate (hereinafter referred to as DCP-A) as component (B) 31.0 parts, triethylamine (hereinafter referred to as TEA) 0.01 part, and methoquinone 0.2 part were added and heated to 60 ° C. with stirring, and tetraethylene glycol bis (3- Mercaptopropionate) (hereinafter, EG-MP, corresponding to the above general formula (3); x = 186 calculated by formula 1) 19.0 parts of toluene and 19.0 parts of toluene were added from the dropping funnel for 2 hours. The whole amount was added dropwise. Then, it kept at 60 degreeC for 5 hours, and obtained the bifunctional acrylate (resin 1) containing the thioether bond which has the terminal structure of General formula (1).

<Synthesis Example 2>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet and dropping funnel, 30.8 parts of butyl acetate, 2-hydroxy-3-acryloyloxypropyl methacrylate (product) Name “NK Ester 701A” Shin-Nakamura Chemical Co., Ltd.) 30.8 parts, 0.01 parts TEA, 0.2 parts methoquinone and heated to 60 ° C. with stirring, as component (A) prepared in advance A mixed solution of 19.2 parts of trimethylolpropane tris (3-mercaptopropionate) (hereinafter TM-MP, corresponding to the above general formula (4); x = 133) and 19.2 parts of butyl acetate was added to a dropping funnel. The whole amount was added dropwise over 2 hours. Then, it kept at 60 degreeC for 5 hours, and obtained the trifunctional methacrylate (resin 2) containing the thioether bond which has the terminal structure of General formula (1).

<Synthesis Example 3>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet and dropping funnel, 31.9 parts of butyl acetate, tetraethylene glycol diacrylate (hereinafter, 4EGA) 31.9 as component (B) Part, TEA 0.01 part, methoquinone 0.2 part, heated to 60 ° C. with stirring, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate as component (A) prepared in advance (Hereinafter, TI-MP, corresponding to the above general formula (5); x = 176) 18.1 parts and a mixed solution of 18.1 parts of butyl acetate were added dropwise from the dropping funnel over 2 hours. Thereafter, the mixture was kept at 60 ° C. for 5 hours to obtain a thioether bond-containing trifunctional acrylate (resin 3) having a terminal structure of the general formula (1).

<Synthesis Example 4>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet and dropping funnel, 39.8 parts of toluene, 39.8 parts of tripropylene glycol diacrylate (hereinafter, TPGDA) as component (B) , 0.01 parts of TEA, 0.2 parts of methoquinone and heated to 60 ° C. with stirring, pentaerythritol tetrakis (3-mercaptopropionate) as the component (A) prepared in advance, hereinafter PT-MP, Corresponding to the above general formula (6); x = 123) 10.7 parts of a mixed solution of 10.7 parts of toluene was added dropwise over 2 hours from the dropping funnel. Thereafter, the mixture was kept at 60 ° C. for 5 hours to obtain a thioether bond-containing tetrafunctional acrylate (resin 4) having a terminal structure of the general formula (1).

<Synthesis Example 5>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet and dropping funnel, 35.6 parts of butyl acetate, 35.6 parts of NK ester 701A as component (B), 0.01 part of TEA, 0.2 parts of methoquinone was added and heated to 60 ° C. with stirring. Dipentaerythritol hexakis (3-mercaptopropionate), hereinafter DP-MP, the above general formula (7) was prepared as component (A) prepared in advance. X = 131) A mixed solution of 14.4 parts and 14.4 parts of butyl acetate was added dropwise over 2 hours from the dropping funnel. Thereafter, the mixture was kept at 60 ° C. for 5 hours to obtain a thioether bond-containing hexafunctional methacrylate (resin 5) having a terminal structure of the general formula (1).

<Example 1>
50 parts of pentaerythritol triacrylate (hereinafter referred to as PE3A), photopolymerization initiator (trade name “Irgacure 184” BASF) with respect to 100 parts of the bifunctional acrylate (resin 1) containing the thioether bond obtained in Synthesis Example 1. 5 parts and 95 parts of methyl ethyl ketone (hereinafter, MEK) were blended to prepare an active energy ray-curable hard coat resin composition having a solid content of 40%.

<Example 2>
To 100 parts of the thioether bond-containing trifunctional methacrylate (resin 2) obtained in Synthesis Example 2, 116.7 parts of PE3A, 8.3 parts of Irgacure 184, 191.7 parts of MEK were blended, and the solid content was 40. % Active energy ray-curable hard coat resin composition.

<Example 3>
50 parts of hexafunctional urethane acrylate (trade name “UA-306H”; Kyoeisha Chemical Co., Ltd.) and 5 parts of Irgacure 184 with respect to 100 parts of trifunctional methacrylate (resin 2) containing thioether bond obtained in Synthesis Example 2 , 95 parts of MEK was blended to obtain an active energy ray-curable hard coat resin composition having a solid content of 40%.

<Example 4>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet and dropping funnel, 39.5 parts of methyl isobutyl ketone was added and heated to 110 ° C. under a nitrogen stream, and then glycidyl methacrylate. (Hereinafter referred to as GMA) 26.0 parts and azobisisobutyronitrile 1.2 parts in total are dropped over 2 hours from a dropping funnel charged with a mixed solution and reacted for 5 hours to obtain a GMA copolymer. It was. Thereafter, after cooling to room temperature, 13.2 parts of acrylic acid, 0.3 part of triphenylphosphine and 0.1 part of methoquinone were added, the dropping funnel was removed, the nitrogen inlet was replaced with an air bubbling device, and air was removed. The mixture was stirred while bubbling and reacted at 110 ° C. for 6 hours to obtain a polyester acrylate having a weight average molecular weight of 17,000. To 125 parts of this polyester acrylate, 100 parts of thioether bond-containing trifunctional methacrylate (resin 2) obtained in Synthesis Example 2 is blended with 5 parts of Irgacure 184 and 20 parts of MEK, and the activity is 40% solids. An energy ray curable hard coat resin composition was obtained.

<Example 5>
To 100 parts of the thioether bond-containing trifunctional acrylate (resin 3) obtained in Synthesis Example 3, 116.7 parts of PE3A, 8.3 parts of Irgacure 184, 191.7 parts of MEK were blended, and the solid content was 40%. Active energy ray-curable hard coat resin composition.

<Example 6>
For 100 parts of thioether bond-containing tetrafunctional acrylate (resin 4) obtained in Synthesis Example 4, 50 parts of glycerin triacrylate (trade name “Denacol DA-314”; Nagase Chemical Industries Ltd.), 5 parts of Irgacure 184 , 95 parts of MEK was blended to obtain an active energy ray-curable hard coat resin composition having a solid content of 40%.

<Example 7>
Ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate (trade name “NK Ester A” with respect to 100 parts of the thioether bond-containing hexafunctional methacrylate (resin 5) obtained in Synthesis Example 5 −9300-1CL ”; Shin-Nakamura Chemical Co., Ltd.) 50 parts, Irgacure 184 5 parts, and 95 parts of MEK were blended to obtain an active energy ray-curable hard coat resin composition having a solid content of 40%.

<Comparative Example 1>
Pentaerythritol triacrylate (PE3A), which is known as a component of a general hard coat agent, is used for comparison. As PE3A, a mixture of 100 parts of a trade name “Aronix M305” (manufactured by Toagosei Co., Ltd.), 5.0 parts of Irgacure 184, and 145 parts of MEK is used as a general-purpose hard coating agent having a solid content of 40%. And Comparative Example 1 was obtained.

<Comparative example 2>
For the purpose of imparting flexibility by reducing the crosslinking density, a part of the resin composition of Comparative Example 1 was substituted with a monofunctional acrylic monomer; isobornyl acrylate. 25.0 parts of Aronix M305, 75.0 parts of isobornyl acrylate, 5.0 parts of Irgacure 184, and 145 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.

<Comparative Example 3>
For the purpose of imparting flexibility, the resin composition of Comparative Example 1 was blended with an unreacted resin having no radical polymerizable group. Aronix M305 80 parts, saturated polyester resin Trade name “KA-2056” (Arakawa Chemical Co., Ltd.) 33.3 parts (solid content 20.0 parts), Irgacure 184 5 parts, MEK 131.7 parts are mixed and solid A 40% active energy ray resin composition was obtained.

<Comparative example 4>
100 parts of UA-306H, 5 parts of Irgacure 184, and 145 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.

<Comparative Example 5>
100 parts of Denacol DA-314, 5 parts of Irgacure 184, and 145 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.

<Comparative Example 6>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet and dropping funnel, 39.5 parts of methyl isobutyl ketone was added and heated to 110 ° C. under a nitrogen stream, and then glycidyl methacrylate. (Hereinafter referred to as GMA) 26.0 parts and azobisisobutyronitrile 1.2 parts in total are dropped over 2 hours from a dropping funnel charged with a mixed solution and reacted for 5 hours to obtain a GMA copolymer. It was. Thereafter, after cooling to room temperature, 13.2 parts of acrylic acid, 0.3 part of triphenylphosphine and 0.1 part of methoquinone were added, the dropping funnel was removed, the nitrogen inlet was replaced with an air bubbling device, and air was removed. The mixture was stirred while bubbling and reacted at 110 ° C. for 6 hours to obtain a polyester acrylate having a weight average molecular weight of 17,000. 2 parts of Irgacure 184 was blended with 100 parts of this polyester acrylate to obtain an active energy ray-curable hard coat resin composition having a solid content of 40%.

<Comparative Example 7>
100 parts of NK ester A-9300-1CL, 5 parts of Irgacure 184, and 145 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.

<Comparative Example 8>
As a multifunctional acrylate having flexibility, ε-caprolactone-modified dipentaerythritol hexaacrylate; trade name “DPCA-120” (Nippon Kayaku Co., Ltd.) 100 parts, Irgacure 184 5 parts, MEK 145 parts are mixed and solid A 40% active energy ray resin composition was obtained.

<Comparative Example 9>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet, 15.9 parts isophorone diisocyanate, polycarbonate diol (number average molecular weight 1000, trade name “Duranol T6001” Asahi Kasei Chemicals) 35.8 parts Then, 40 parts of methyl isobutyl ketone was added, heated to 60 ° C. with stirring and kept for 1 hour, then 0.05 parts of dibutyl tin diacetate was added and reacted at 80 ° C. for 2 hours, both ends of the OH group of the polycarbonate diol. Each was added with isophorone diisocyanate to introduce isocyanate groups at both ends of the polycarbonate. Thereafter, the mixture was cooled to 40 ° C., 8.3 parts of 2-hydroxyethyl acrylate and 0.05 part of dibutyltin diacetate were added, heated to 80 ° C., reacted for 5 hours, and 2-hydroxyethyl acrylate was added to the isocyanate terminal. OH group was added to obtain polycarbonate urethane diacrylate (resin 6). After cooling to room temperature, 5 parts of Irgacure 184 and 47 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.

The hard coating agent of each Example and Comparative Example was coated with a bar coater No. 1 on the easy-adhesion surface of a single-side easy-adhesion-treated polyethylene terephthalate film (trade name “Cosmo Shine A4100” Toyobo Co., Ltd.) having a thickness of 188 μm. After coating at 12 and drying at 80 ° C. for 1 minute, UV light was irradiated at 300 mJ / cm ² to obtain a cured film having a thickness of 5 μm.

The cured film prepared using the hard coating agent of each Example and Comparative Example was evaluated by a pencil hardness test and a scratch resistance test as an evaluation of the hard coat property. The workability was evaluated by the elongation and flexibility calculated by a tensile test in which the cured film was stretched in one direction. The evaluation results are shown in Table 3.

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

(Evaluation of scratch resistance)
Using # 0000 steel wool, a load of 100 g / cm ² was applied, the cured film surface was scratched 10 times, and the presence or absence of scratches was confirmed visually. If there were no scratches, it had excellent hard coat properties, and if it was several scratches, it could be used as a hard coating agent, and many scratches were evaluated as unsuitable results as a hard coating agent.

(Elongation)
For the elongation, a test piece obtained by cutting a cured film into a strip shape having a length of 100 mm and a width of 7 mm was set in a tensile tester (model number “RTC-1250A”, Orientec Co., Ltd.) with a chuck distance of 50 mm, and a room temperature of 25 ° C. The test was carried out at a tensile rate of 10 mm / min in an environment with a humidity of 45% RH, and the distance between chucks became 60 mm (elongation 20%), 65 mm (elongation 30%), and 70 mm (elongation 40%), respectively. And visually observe the presence or absence of cracks in the cured film. When there was no crack, it was evaluated as “good”, and when a crack occurred, it was evaluated as “poor”. By measuring the elongation of the cured film, the flexibility of the cured film can be evaluated. If the elongation is large, it can be said to be a flexible cured film. For example, in the molding process of a coating film, it can flexibly follow the stress of stretching, so that cracks in the cured film can be suppressed, contributing to workability. be able to.

(Evaluation of flexibility)
The surface of the cured film was turned outward, wound around a φ2 mm cylinder, and the presence or absence of cracks was visually confirmed. When there was no crack, it was marked as “◯” and when there was a crack, it was marked as “X”.

Claims (8)

(Meth) acryloyl group having x at 100 calculated from Formula 1 at the thiol terminal of the polyfunctional thiol compound (A) and at least one terminal of the bifunctional (meth) acrylate compound (B) Is a polyfunctional thio (meth) acrylate resin, which is formed by an ene-thiol reaction and has two or more terminal structures represented by the general formula (1).
(In the formula, X represents a structure excluding the terminal thiol group of the polyfunctional thiol compound (A). R ₁ and R ₃ are each hydrogen or a methyl group, R ₂ is O, or —O—R ₉ —O—. R ₉ represents a C1-20 linear or branched alkylene group, — (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 general formula (1-1) to (1-3 ) M, p and q are positive integers and p + q = 2-6.)
(Meth) acryloyl group having x at 100 calculated from Formula 1 at the thiol terminal of the polyfunctional thiol compound (A) and at least one terminal of the bifunctional (meth) acrylate compound (B) Is a polyfunctional thio (meth) acrylate resin having a terminal structure represented by the following general formula (2) bonded by an ene-thiol reaction.
(In the formula, X represents a structure excluding the terminal thiol group of the polyfunctional thiol compound (A). R ₁ and R ₃ are each hydrogen or a methyl group, R ₂ is O, or —O—R ₉ —O—. R ₉ represents a C1-20 linear or branched alkylene group, — (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 general formula (1-1) to (1-3 ) M, p and q are positive integers and p + q = 2-6.)
The polyfunctional thiol compound (A) according to claim 1 or 2, wherein the polyfunctional thiol compound (A) contains at least one of polyfunctional thiol compounds represented by the following general formulas (3) to (7). (Meth) acrylate resin.
(In the formula, R ₄ represents hydrogen or a methyl group, and n represents an integer of 1 to 12.)
(In the formula, R ₅ represents hydrogen or a methyl group.)
(In the formula, R ₆ represents hydrogen or a methyl group.)
(In the formula, R ₇ represents hydrogen or a methyl group.)
(In the formula, R ₈ represents hydrogen or a methyl group.) An activity comprising the polyfunctional thio (meth) acrylate resin according to any one of claims 1 to 3, a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups, and a photopolymerization initiator. Energy ray curable hard coat resin composition. A cured film obtained by curing the active energy ray-curable hard coat resin composition according to claim 4 by irradiation with active energy rays. A plastic film in which the cured film according to claim 5 is laminated. A plastic injection molded product using the plastic film according to claim 6. The processed product which laminated | stacked the plastic film of Claim 6.