KR20130102004A - Polyfuntional thio(meth)acrylate resin, active-energy-ray curable hard coating resin composition containing the same, cured film obtained by curing the composition, plastic film laminated the cured film, injection molded article using the plastic film and processed products - Google Patents

Abstract

[화학식 1]

(1)
(식 중에서, X는 다관능 티올 화합물(A)의 말단 티올기를 제외하는 구조를 나타낸다. R₁ 및 R₃은 각각 수소 또는 메틸기, R₂는 Ｏ 또는 -Ｏ-R₉-Ｏ-를 나타낸다. R₉는, Ｃ1∼20의 직쇄상 또는 분기상의 알킬렌기, -(ＣＨ₂ＣＨ₂Ｏ)ｍＣＨ₂ＣＨ₂-, -(ＣＨ₂ＣＨ(ＣＨ₃)Ｏ)ｍＣＨ₂ＣＨ(ＣＨ₃)-, -ＣＨ₂ＣＨ₂ＯＰ=Ｏ(ＯＨ)ＯＣＨ₂ＣＨ₂-, -ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂- 및 하기 일반식(1-1)∼(1-3)으로 표현되는 구조로부터 선택되는 적어도 일종이다. m, p 및 q는 양의 정수, p + q = 2∼6을 나타낸다.)

(1-1)

(1-2)

(1-3)(Purpose) The present invention provides a polyfunctional thio (meth) acrylate resin having a high hardness and abrasion resistance, which is capable of forming a highly flexible cured film having excellent hard coating properties and high elongation and flexibility. It aims to provide.
(Solution means) It is provided in the thiol terminal of the polyfunctional thiol compound (A) which has a value of 100 or more and 200 or less calculated by Formula (1), and at least one terminal of the bifunctional (meth) acrylate compound (B). The polyfunctional thio (meth) acrylate resin which has a (meth) acryloyl group made by en-thiol reaction, and has two or more terminal structures represented by General formula (1) is used.
[Number 1]

[Formula 1]

(One)
(Wherein X represents a structure excluding terminal thiol groups of the polyfunctional thiol compound (A). R ₁ and R ₃ each represent hydrogen or a methyl group, and R ₂ represents O or —O—R ₉ —O—. R ₉ is an alkylene group linear or branched _{C1~20, - (CH 2 CH 2} O) mCH 2 CH 2 -, - (CH 2 CH (CH 3) O) mCH 2 CH (CH 3) -, At least one selected from the structures represented by -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). M, p, and q represent a positive integer, p + q = 2-6.)

(1-1)

(1-2)

(1-3)

Description

Polyfunctional thio (meth) acrylate resin, active energy ray hardening type hard coat resin composition containing this, cured film obtained by hardening this, plastic film laminated | stacked cured film, plastic injection molded article and processed product using a plastic film {POLYFUNTIONAL THIO ( METH) ACRYLATE RESIN, ACTIVE-ENERGY-RAY CURABLE HARD COATING RESIN COMPOSITION CONTAINING THE SAME, CURED FILM OBTAINED BY CURING THE COMPOSITION, PLASTIC FILM LAMINATED THE CURED FILM, INJECTION MOLDED ARTICLE USING THE PLASTIC ED PRODUCT AND

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

(1) Decorative hard coating for laminating an adhesive layer, a pattern layer, and a hard coating layer on a plastic film such as PET (polyethylene terephthalate) as a decorative method for imparting a pattern or feel to the surface of a plastic product. In-mold molding method in which a film is inserted into a mold and attached to a plastic molded product at the same time as injection molding (called molds, etc.) or plastics produced by (2) injection molded plastics (II-MｏｌｄＬａｎａｔｉｎｇ) Attention has been paid to a film attachment method for bonding a decorative hard coat film to a product surface, a steel sheet, and a building material.

In the above method, the decorative hard coat film is stretched to conform to the mold inner surface or the product shape of the molded article. However, in general, since the hard coating property is prioritized to become hard and brittle, the decorative hard coating film used in the above-described method tends to generate cracks due to stress at the time of elongation, thereby degrading workability. Specifically, cracks are likely to occur due to severe curved processing or box-like processing (called deep drawing processing), so that the workability is improved by providing flexibility instead of deteriorating hard coating property or Design was limited.

In recent years, in order to differentiate a product, the complexity of a design and the scratch resistance of a surface are calculated | required, and both the flexibility and hard-coating property in a hard coat film are indispensable. Various methods have been proposed for this. For example, the method of controlling the crosslinking density by the compounding composition of a trifunctional or more (meth) acryl oligomer and a 1-2 functional (meth) acrylic monomer is mentioned (refer patent document 1). According to this method, a hard coating film having high surface hardness and flexibility capable of following deformation during molding is obtained, but surface hardness and flexibility have become a trade-off relationship, and a certain balance is achieved. There was a problem that it was compelled to compromise.

As another example, a polymer (meth) acrylate having a molecular weight of 5,000 to 50,000 (meth) acryloyl equivalents of 200 g / ｑ or more and 800 g / ｑ or less, and (meth) acryloyl having a molecular weight of 1,000 to 10,000 A method of blending a polyfunctional urethane (meth) acrylate having an equivalent weight of 100 g / eV or more and less than 200 g / eV is proposed (see Patent Document 2). However, also in this, the balance of hard coatability and the trade-off of flexibility is prescribed | regulated in (meth) acryloyl equivalent, and it is compelled to compromise with some balance.

Moreover, the method of providing workability by mix | blending non-reactive resin which does not have a radically polymerizable double bond with a (meth) acrylic monomer is also proposed (refer patent document 3). However, when blending such a non-reactive resin or a plastic resin, the processability to be softened is improved, but it is difficult to reach the recently required high hard coating property.

Japanese Patent Laid-Open No. 2011-148964

Japanese Patent Laid-Open No. 2004-123780

Japanese Patent Laid-Open No. 2008-208154

An object of this invention is to provide the polyfunctional thio (meth) acrylate resin which can form the cured film which is hard-coating and high in flexibility, and excellent in workability.

 That is, this invention 1 is the thiol terminal of the polyfunctional thiol compound (A) (Hereinafter, it is also called (A) component) whose polyhydric value calculated by (1) is 100-200, and a bifunctional (meth) acryl. The (meth) acryloyl group provided in at least one terminal of a late compound (B) (henceforth a (B) component) is formed by en-thiol reaction, and the terminal structure represented by General formula (1) is 2 It is a polyfunctional thio (meth) acrylate resin provided above.

[Number 1]

[Formula 1]

(1)

(One)

(Wherein X represents a structure excluding terminal thiol groups of the polyfunctional thiol compound (A). R ₁ and R ₃ each represent hydrogen or a methyl group, and R ₂ represents O or —O—R ₉ —O—. R ₉ is a straight chain of C1~20 (直鎖狀) or branched alkylene group (分岐狀), - (CH 2 CH 2 O) mCH 2 CH 2 -, - (CH 2 CH (CH 3) O _{) mCH 2 CH (CH 3)} -, -CH 2 CH 2 OP = O (OH) OCH 2 CH 2 -, -CH 2 CH (OH) CH 2 - , and the following formulas (1-1) to (1- It is at least one selected from the structure represented by 3), m, p and q represent a positive integer, p + q = 2-6.)

(1-1)

(1-1)

(1-2)

(1-2)

(1-3)

(1-3)

The present invention 2 is a terminal represented by the following general formula (2) in which the thiol terminal of the component (A) and the (meth) acryloyl group included in at least one terminal of the component (B) are bonded by en-thiol reaction. It is a polyfunctional thio (meth) acrylate resin which has a structure.

[Formula 2]

(2)

(2)

(Wherein X represents a structure excluding terminal thiol groups of the polyfunctional thiol compound (A). R ₁ and R ₃ each represent hydrogen or a methyl group, and R ₂ represents O or —O—R ₉ —O—. R ₉ is an alkylene group linear or branched _{C1~20, - (CH 2 CH 2} O) mCH 2 CH 2 -, - (CH 2 CH (CH 3) O) mCH 2 CH (CH 3) -, At least one selected from the structures represented by -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). M, p, and q represent a positive integer, p + q = 2-6.)

(1-1)

(1-1)

(1-2)

(1-2)

(1-3)

(1-3)

This invention 3 is a polyfunctional thio (meth) acrylate resin whose (A) component is either of the polyfunctional thiol compound represented by following General formula (3)-(7) in this invention 1 or 2. .

(3)

(In formula, R <_4> is hydrogen or a methyl group and n shows the integer of 1-12.)

[Formula 4]

(In formula, R <_5> represents hydrogen or a methyl group.)

[Chemical Formula 5]

(In formula, R <_6> represents hydrogen or a methyl group.)

[Formula 6]

(In formula, R <_7> represents hydrogen or a methyl group.)

[Formula 7]

(In formula, R <_8> represents hydrogen or a methyl group.)

This invention 4 is an activity containing the polyfunctional thio (meth) acrylate resin in any one of this invention 1-3, the polyfunctional (meth) acrylate which has three or more (meth) acryloyl groups, and a photoinitiator. It is an energy radiation curable hard coating resin composition.

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

This invention 6 is a plastic film in which the cured film of this invention 5 was laminated.

This invention 7 is a plastic injection molded article using the plastic film of this invention 6.

This invention 8 is the processed product which laminated | stacked the plastic film of this invention 6.

By using the thioether bond-containing polyfunctional thio (meth) acrylate resin of the present invention, both flexibility and excellent hard coating property (excellent surface scratching difficulty) with high pencil hardness and scratch resistance are achieved. One cured film can be formed. Thereby, the hard-coating film which is difficult by the conventional technique and which can provide not only high workability but also scratch resistance of the cured film surface can be formed.

(A) component in this invention is not specifically limited, if it is not a monofunctional thiol compound, but is a polyfunctional thiol compound which has two or more thiol groups (-SH) at the terminal as a reactive functional group. By making (A) component a polyfunctional thiol compound, the resin of this invention can be made into the polyfunctional thio (meth) acrylate resin provided with two or more (meth) acryloyl groups at the terminal, and irradiates an active energy ray Since the hardened | cured material obtained by making it easy to take a dense three-dimensional crosslinked structure can be provided with the outstanding hard-coating property. The polyfunctional thio (meth) acrylate resin in this specification means the polyfunctional (meth) acrylate containing 2 or more thioether bond.

The component (A) may have a polyfunctional thio (meth) acrylate resin that forms a cured film having excellent hard coatability, which is a value of 100 to 200 calculated by the formula (1). It is preferable at the point. If x is from 100 to 200, a dense three-dimensional crosslinked structure can be obtained, which can impart better hard coating properties. As a specific example, tetraethylene glycol bis (3-mercapto propionate) represented by general formula (3)-(7), trimethylol propane tris (3-mercapto propionate), tris-[(3-mer Polyfunctional thiol compounds such as captopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol hexakis (3-mercaptopropionate), and the like. These can be used 1 type or in mixture of 2 or more types. From the point of availability, the polyfunctional thiol compound represented by General Formula (3)-(7) is more preferable.

[Number 1]

The said (B) component will not be specifically limited if it is a bifunctional (meth) acrylate which has a (meth) acryloyl group in at least one terminal. In the case of using a trifunctional or more than one polyfunctional (meth) acrylate compound, the crosslinking structure between molecules is easily formed by an ene-thiol reaction with the polyfunctional thiol compound, resulting in gelation. Is likely 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) acrylic Latex, neopentylglycol di (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 3-methyl-1.5-pentanedioldi (meth) acrylate, 1.6-hexanedioldi (meth) acrylate , 2-butyl-2-ethyl-1.3-propanedioldi (meth) acrylate, 1.9-nonanedioldi (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, EO or PO modified bisphenol A di (meth) acrylate compound, hydroxy pivalate neopentyl glycol di (meth) acrylate, 2-hydroxy-3- acryloyloxypropyl methacrylate, di (meth) acrylic acid anhydride, etc. are mentioned. . You may mix these individually or in combination of 2 or more types, respectively. More preferably, tripropylene glycol di (meth) acrylate, dimethylol tricyclodecanedi (meth) acrylate, and 2-hydroxy-3-acryloyloxypropyl methacryl are readily available. It is a latex and di (meth) acrylic-acid anhydride. When using 2 or more types, the use ratio of each bifunctional (meth) acrylate component is not specifically limited.

In this invention, the said en-thiol reaction means addition reaction of the reactive unsaturated group of a (meth) acryloyl compound with the thiol group of a thiol compound. The polyfunctional thio (meth) acrylate of this invention does not contain the radical copolymer by the radical copolymerization reaction of the said (A) component and (B) component. When it is a radical copolymer, the structure of General formula (1) which this invention has is not included, and the long-chain polymer only of (B) component couple | bonded with the thiol terminal of (A) component, and hard-coating property is improved. However, workability tends to decrease.

As for the polyfunctional thio (meth) acrylate resin of this invention, the (meth) acryloyl group with which the terminal thiol group (-SH) of the said (A) component and at least one terminal of (B) component is equipped with It is a product obtained by thiol reaction, and is provided with two or more terminal structures represented by General formula (1). The use ratio of the (B) component in the polyfunctional thio (meth) acrylate resin of this invention is 1 bifunctional (meth) acrylate compound of (B) component with respect to one thiol group of (A) component. The ratio which becomes -3 molecule is preferable. By setting the ratio of the component (B) to this ratio, not only the increase in unreacted component (B) can be suppressed and the hard coating property can be made better, but also the probability that both ends of the component (B) react with the thiol group. Lowers the molecular weight, prevents the increase of the molecular weight, prevents the high viscosity, has good compatibility with organic solvents, etc., and also becomes difficult to gel. More preferably, the use ratio of (B) component is 1-2 molecules from the point which makes it compatible with the workability of hardened | cured material, and hard-coating property.

Although the en-thiol reaction is highly reactive, the reaction proceeds even without a catalyst, but it is preferable to use an acid or an amine catalyst. Specifically, for example, tin compounds such as octylic acid tin, dibutyltin dilaurate, and the like as acid catalysts, and amine catalysts include triethylamine, imidazolidine, proline, Cinchona alkaloid, triazabicyclodecene, diazabicycloundecene, hexahydromethylpyrimidopyrimidine, diazabicyclononane, tetramethylguanidine, diazabicyclooctane, diisopropylethylamine, tetramethylpy Ferridine. These may be used individually by 1 type, and may mix and use 2 or more types. Moreover, it is preferable that the usage-amount of the said catalyst is about 0.001-0.01 weight part with respect to 100 weight part of prepolymerization components.

In the en-thiol reaction, a polymerization inhibitor such as metoquinone, hydroquinone, trimethylhydroquinone and N-nitrosophenylhydroxylamine can be used. Although the usage-amount of a polymerization inhibitor is not specifically limited, It is preferable to set it as about 1 weight part or less normally with respect to 100 weight part of total weight of a product, in order not to adversely affect the reaction hardenability of obtained resin. In order to prevent polymerization, air may be sucked into the reaction system.

In the en-thiol reaction, the product can be obtained without using an organic solvent. In addition, it is also possible to synthesize in a solvent using an organic solvent in which each component is soluble, and in this case, there is an advantage that a product can be obtained at low viscosity by the dilution effect of the organic solvent. As a preferable organic solvent, if it is organic solvents other than ketones, such as methyl ethyl ketone, methyl isobutyl ketone, etc., it will not specifically limit, A well-known thing can be used. When ketones are used, the en-thiol reaction of the thiol group of (A) component and the (meth) acryloyl group of (B) component is inhibited. As a suitable organic solvent, Specifically, Alcohol, such as propanol and butanol; Aromatic hydrocarbons such as toluene and benzene; Butyl acetate, ethyl acetate, etc. are mentioned, These may be used individually by 1 type, and may mix and use 2 or more types. In each reaction step, when the reaction temperature is set high, since the reaction can be efficiently carried out in a short time, a high boiling point is preferable. However, considering that a good dryness is preferable as the active energy ray-curable hard coating agent, ethyl acetate is preferred. , Butyl acetate and toluene are preferable.

The present invention further provides a thioether bond having a terminal structure represented by the following general formula (2) in which a thiol terminal of component (A) and at least one (meth) acryloyl group of component (B) are bonded by en-thiol reaction. It is also a polyfunctional thio (meth) acrylate resin containing.

[Formula 2]

(Wherein X represents a structure excluding terminal thiol groups of the polyfunctional thiol compound (A). R ₁ and R ₃ each represent hydrogen or a methyl group, and R ₂ represents O or —O—R ₉ —O—. R ₉ is an alkylene group linear or branched _{C1~20, - (CH 2 CH 2} O) mCH 2 CH 2 -, - (CH 2 CH (CH 3) O) mCH 2 CH (CH 3) -, At least one selected from the structures represented by -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). M, p, and q represent a positive integer, p + q = 2-6.)

(1-1)

(1-1)

(1-2)

(1-2)

(1-3)

(1-3)

The polyfunctional thio (meth) acrylate resin of this invention is equipped with the terminal structure in brackets of 2-6 in 1 molecule as represented by General formula (2). If there is only one structure shown in parentheses, the hard coatability of a cured film will fall. If the structure shown in parentheses is 2-6, a dense three-dimensional bridge | crosslinking structure will be built up, and hard-coating property will improve. When the structure shown in parentheses exceeds 6, it will become difficult to control en-thiol reaction and will gelatinize easily.

(A) component and (B) component in the polyfunctional thio (meth) acrylate resin of this invention, these ratios, and a manufacturing method are as above-mentioned.

An active energy ray-curable hard coating resin composition containing the polyfunctional thio (meth) acrylate resin, a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups, and a photopolymerization initiator is also one of the present inventions. . Since the hardened | cured material of the active energy ray hardening-type hard-coating resin composition of this invention has high crosslinking density, it is excellent in hard coat property and also excellent in flexibility. Therefore, both the hard coatability of the cured film and the flexibility which were difficult by the method of adjustment of the crosslinking density currently considered, the compounding of unreacted resin, etc. can be achieved, and it is used suitably for the member for decorative hard coat films. Can be.

The polyfunctional (meth) acrylate having three or more (meth) acryloyl groups is not particularly limited as long as it is (meth) acrylate having three or more terminals of the (meth) acryloyl group in one molecule. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolpropaneethoxy tri (meth) acrylate, glycerin ethoxy tri (meth) acrylate, glycerin propoxytri (meth) acrylate, and ethoxylated iso Cyanuric tri (meth) acrylate, ε-caprolactone modified tris- (2- (meth) acrylooxyethyl) isocyanurate, pentaerythritol tree / tetra (meth) acrylate, pentaerythritol ethoxy tree / Tetra (meth) acrylate, pentaerythritol propoxytri / tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythr Hexa (meth) acrylate, lactone-ε- caprolactone-modified dipentaerythritol hexa (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate. You may mix these individually or in combination of 2 or more types, respectively. From the viewpoint of hard coating property and curability, pentaerythritol tri / tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin propoxytrityl (meth) acrylate, ε-caprolactone modified tris- (2- (meth) acrylooxyethyl) isocyanurate, urethane (meth) acrylate, and polyester (meth) acrylate. More preferably, they are urethane (meth) acrylate, pentaerythritol tri / tetra (meth) acrylate, and polyester (meth) acrylate. When using 2 or more types, the use ratio of each polyfunctional (meth) acrylate component is not specifically limited.

As said urethane (meth) acrylate, three in a molecule | numerator obtained by making hydroxyl group containing (meth) acrylate react with the terminal isocyanate group containing compound obtained by making a polyhydric isocyanate compound and two or more hydroxyl group containing compounds react. Three or more (meth) acryloyl groups in a molecule | numerator obtained by making the urethane (meth) acrylate which has the above (meth) acryloyl group, and the (meth) acrylate compound containing a polyhydric isocyanate compound and one hydroxyl group react Urethane (meth) acrylate etc. which are provided are mentioned.

As polyester (meth) acrylate, the epoxy (meth) acrylate etc. which have three or more (meth) acryloyl groups obtained by making (meth) acrylic acid react with the compound containing three or more epoxy groups in a molecule | numerator are mentioned. Can be.

As said photoinitiator, if it can decompose | disassemble by ultraviolet-ray and generate | occur | produce a radical and can start superposition | polymerization, it will not specifically limit but a well-known thing can be used. Specifically, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- On, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylforce Pin oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, and the like, and the like can be easily obtained from BASF. These can be used individually by 1 type or in combination of 2 or more type. It is preferable that the usage-amount of a photoinitiator shall be about 0.1-10 weight part with respect to 100 weight part of active energy ray hardening-type resin compositions.

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 properties. As the inorganic filler, known ones such as silica and metal oxide fine particles can be used without limitation. For example, titanium oxide, aluminum oxide, antimony oxide, tin oxide, zirconium oxide, zinc oxide, cerium oxide, indium oxide, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more type. Among them, silica, titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide are preferred because the commercial product range is faithful, readily available, and inexpensive.

It is preferable to use what controlled the average particle diameter of the said inorganic filler below 200 nm (by laser diffraction and scattering method). When the average particle diameter exceeds 200 nm, whitening is likely to occur in the cured film, which may damage optical characteristics such as haze and transmission efficiency.

The active energy ray hardening type hard coat resin composition of this invention can further mix | blend an additive as needed. Examples of the additives 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 hardening | curing 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 this invention is used, it can be used as a decorative hard coating film compatible with workability and hard coating property.

Examples of the active energy rays include light (rays such as ultraviolet rays), electron beams, X rays, α rays, β rays, γ rays, neutron rays, and the like. In general, light and an electron beam are preferable at the point that it is widely spread.

The plastic film in which the cured film is laminated is also one of the present invention. It is also possible to cope with the rough processing and the deep drawing processing which were not applicable to the crack of the hard coating layer so far, and can provide the hard coating property of the scratch which is equivalent to the conventional one on the surface of a molded article. Specifically, it can be used suitably for an IML method and a film bonding decoration.

There is no restriction | limiting in particular as a base material of the said plastic film, For example, plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, an epoxy resin, a melamine resin, a triacetyl cellulose resin, AAS resin , AS resins, norbornene-based resins, and the like.

As a method of laminating | stacking a cured film on the said plastic film, after apply | coating an active energy ray hardening-type hard-coating resin composition and drying by a well-known method, it is made to irradiate and harden an active energy ray. Examples of the method for applying the resin composition include bar coater coating, meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, and flexographic printing. flexographic printing, screen printing, and the like. In addition, the application amount is not particularly limited, but in general, the weight after drying is in the range of 0.1 to 20 g / m ² , preferably 0.5 to 10 g / m ² .

The present invention is also a plastic injection molded article using the plastic film. Conventionally, due to the problem of cracking of the hard coating layer, there has been a compromise on the hard coating properties of plastic injection-molded articles or design limitations. An injection molded product can be obtained, and it can be used for a frame of an electric device such as a cellular phone terminal or a PC, a part of an interior trim or an exterior cover in a car.

The present invention is also a processed product in which the plastic film is laminated. In the method of laminating a plastic film, unlike the method of inserting into a mold and attaching a plastic molded article at the same time as injection molding, the plastic film is bonded to the surface of a plastic processed product in which the thermoplastic resin is injection molded or extruded. Moreover, as a processed product, it can be used for the frame of electric devices, such as a mobile telephone terminal and a PC, a part of interior trim and an exterior cover of a vehicle, and a plastic container.

Although an Example and a comparative example are given to the following, this invention is concretely demonstrated to it, but this invention is not limited to each of these examples. In each example, all parts and percentages are based on weight unless otherwise specified.

&Lt; Synthesis Example 1 &

31.0 parts of toluene and 31.0 parts of dimethylol tricyclodecane diacrylate (hereinafter, DCP-A) as a component (B) were added to a four-necked flask equipped with a stirrer, a thermometer, a reflux cooler, a nitrogen inlet, and a dropping funnel. , 0.01 part of triethylamine (hereinafter, TE) and 0.2 part of metoquinone were added and heated to 60 degrees while stirring, and tetraethylene glycol bis (3-mercaptopropionate) (hereinafter, EB) was prepared as (A) component prepared in advance. -MP, corresponded to the said General formula (3): (x = 186) computed by (1) The whole quantity was dripped over 2 hours from the dropping funnel with 19.0 parts and 19.0 parts of toluene. Thereafter, the mixture was kept at 60 degrees for 5 hours to obtain a bifunctional acrylate (resin 1) containing a thioether bond having a terminal structure of the general formula (1).

Synthesis Example 2

To a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, 30.8 parts of butyl acetate and (B) component 2-hydroxy-3-acryloyloxypropyl methacrylate (trade name "N'ester) 3701 parts of 701A "Shin-Nakamura Chemical Co., Ltd.), 0.01 part of TEA, 0.2 part of metoquinones, heated to 60 degree | times, stirring, trimethylol propane tris (3-mercaptopropionate) (3-component) prepared as (A) prepared previously ( Hereinafter, the whole quantity was dripped at the mixed solution of TMD-MP and 19.2 parts of 19.2 parts of butyl acetate and 19.2 parts of butyl acetates corresponding to the said General formula (4). After that, the mixture was kept at 60 degrees for 5 hours to obtain a trifunctional methacrylate (resin 2) containing a thioether bond having a terminal structure of the general formula (1).

&Lt; Synthesis Example 3 &

31.9 parts of butyl acetate, 31.9 parts of tetraethylene glycol diacrylate (hereafter 4EHA), 0.01 parts of TEA, and metoquinone as a (B) component to a four neck flask equipped with a stirrer, a thermometer, a reflux cooler, a nitrogen inlet, and a dropping funnel. It is heated to 60 degree | times, stirring 0.2 part, stirring, and tris- [(3- mercapto propionyloxy) -ethyl]-isocyanurate (Hereafter, TI-MP, the said General formula (A) component prepared previously Equivalent to 5); x = 176) 18.1 parts of mixed solutions of 18.1 parts of butyl acetate were dripped over 2 hours from the dropping funnel. After that, the mixture was kept at 60 degrees for 5 hours to obtain a trifunctional acrylate (resin 3) containing a thioether bond having a terminal structure of the general formula (1).

Synthesis Example 4

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, 39.8 parts of toluene, 39.8 parts of tripropylene glycol diacrylate (hereinafter referred to as TFT), (0.01 parts of TEA), and metoquinone 0.2 It heats to 60 degree, stirring, and adds pentaerythritol tetrakis (3-mercapto propionate) (Hereafter, it is equivalent to PT-MP and the said General formula (6)) as (A) component prepared previously, x = 123 ) 10.7 parts and the mixed solution of 10.7 parts of toluene were dripped whole quantity over 2 hours from the dropping funnel. After that, the mixture was kept at 60 degrees for 5 hours to obtain a tetrafunctional acrylate (resin 4) containing a thioether bond having a terminal structure of the general formula (1).

Synthesis Example 5

Into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, 35.6 parts of butyl acetate and 35.6 parts of NB ester 701A, 0.01 parts of TEA, and 0.2 parts of metoquinone were added to the 60 ° C while stirring. 14.4 parts of dipentaerythritol hexakis (3-mercaptopropionate) (hereinafter referred to as Dp-MP and the general formula (7); x = 131) as a (A) component prepared beforehand by heating, butyl acetate 14.4 parts of mixed solutions were dripped whole quantity over 2 hours from the dropping funnel. After that, the mixture was kept at 60 degrees for 5 hours to obtain a thioether bond-containing six-functional methacrylate (resin 5) having a terminal structure of the general formula (1).

&Lt; Example 1 >

50 parts of pentaerythritol triacrylate (hereinafter referred to as PE3A) and a photopolymerization initiator (trade name "Irgacure 184" BASF) with respect to 100 parts of thioether bond containing bifunctional acrylate (resin 1) obtained by the synthesis example 1. 5 parts and 95 parts of methyl ethyl ketones (hereafter MEB) were mix | blended and it was set as the active energy ray hardening type hard-coating resin composition of 40% of solid content.

&Lt; Example 2 >

11 parts of PE3A, 8.3 parts of Irgacure 184 and 191.7 parts of MEB were blended with 100 parts of the trifunctional methacrylate (resin 2) containing the thioether bond obtained in Synthesis Example 2 to form an active energy ray-curable solid having a solid content of 40%. A hard coat resin composition was used.

&Lt; Example 3 >

To 100 parts of trifunctional methacrylate (resin 2) containing thioether bond obtained in Synthesis Example 2, 50 parts of 6-functional urethane acrylate (trade name "BA-306H"; Kyoeisha Chemical Co., Ltd.), Irgacure 184 parts and 95 parts of MEV were mix | blended and it was set as the active energy ray hardening type hard coat resin composition of 40% of solid content.

<Example 4>

Into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, 39.5 parts of methyl isobutyl ketone was added, and the temperature was raised to 110 degrees under a nitrogen stream, followed by glycidyl methacrylate (hereinafter, referred to as WMA) 26.0. A YM copolymer was obtained by carrying out the whole dropwise addition over 2 hours from the addition funnel which mixed 1.2 parts of azobisisobutyronitrile liquid mixture for 2 hours, and making it react for 5 hours. Thereafter, after cooling to room temperature, 13.2 parts of acrylic acid, 0.3 part of triphenylphosphine, and 0.1 part of metoquinone were added, the dropping funnel was removed, and the nitrogen inlet was exchanged with an air bubbling device to bubble air. The mixture was stirred and reacted at 110 degrees for 6 hours to obtain a polyester acrylate having a weight average molecular weight of 17,000. To 125 parts of polyester acrylates, 100 parts of thioether bond-containing trifunctional methacrylate (resin 2) obtained in Synthesis Example 2 was mixed, 5 parts of Irgacure 184 and 20 parts of MEB were blended, and the solid content was 40%. To an active energy ray-curable hard coat resin composition.

&Lt; Example 5 >

116.7 parts of PE3A, 8.3 parts of Irgacure 184 and 191.7 parts of MEB were blended with 100 parts of the trifunctional acrylate (resin 3) containing the thioether bond obtained in Synthesis Example 3, and the active energy ray-curing hard having a solid content of 40% It was set as the coating resin composition.

&Lt; Example 6 >

50 parts of glycerin triacrylate (trade name "Denacol DA-314"; Nagase Chemical Co., Ltd.) with respect to 100 parts of thioether bond containing tetrafunctional acrylate (resin 4) obtained by the synthesis example 4, Irgacure 184 5 parts and 95 parts of MB were mix | blended and it was set as the active energy ray hardening type hard-coating resin composition of 40% of solid content.

&Lt; Example 7 >

(Epsilon) epsilon -caprolactone modified tris- (2- (meth) acrylooxyethyl) isocyanurate (brand name ") with respect to 100 parts of hexaether methacrylate (resin 5) containing the thioether bond obtained by the synthesis example 5. NB ester A-9300-1CL ", 50 parts of Shin-Nakamura Chemical Co., Ltd., 5 parts of Irgacure 184, and 95 parts of MEB were mix | blended and it was set as the active energy ray hardening type hard-coating resin composition of 40% of solid content.

&Lt; Comparative Example 1 &

Pentaerythritol triacrylate (PE3A), known as a constituent of a general hard coating agent, was used as a comparison. As a PE3A, 100 parts of brand names "Aronix M305" (made by Dong-A Synthetic Co., Ltd.), 5.0 parts of Irgacure 184, and 145 parts of MEV were mixed as a general-purpose hard coating agent having a solid content of 40%.

&Lt; Comparative Example 2 &

For the purpose of imparting flexibility by reducing the crosslinking density, a part of the resin composition of Comparative Example 1 is a monofunctional acryl monomer; Substituted with isobornyl acrylate. 25.0 parts of aronix M305, 75.0 parts of isobornyl acrylate, 5.0 parts of Irgacure 184, and 145 parts of MEV were mixed to obtain an active energy ray resin composition having a solid content of 40%.

&Lt; Comparative Example 3 &

For the purpose of softness provision, unreacted resin which does not have a radical polymerizable group was mix | blended with the resin composition of the comparative example 1. 80 parts of aronix M305, 33.3 parts of saturated polyester resin brand name "WAA-2056" (Arakawa Chemical Industries, Ltd.), 5 parts of Irgacure 184, and 131.7 parts of MEB were mixed to obtain an active energy ray resin composition having a solid content of 40%.

Comparative Example 4

100 parts of BA-306H, 5 parts of Irgacure 184, and 145 parts of MEB were mixed to obtain an active energy ray resin composition having a solid content of 40%.

&Lt; Comparative Example 5 &

100 parts of Denacol D-314, 5 parts of Irgacure 184, and 145 parts of MEB were mixed to obtain an active energy ray resin composition having a solid content of 40%.

&Lt; Comparative Example 6 >

Into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, 39.5 parts of methyl isobutyl ketone was added, and the temperature was raised to 110 degrees under a nitrogen stream, followed by glycidyl methacrylate (hereinafter, referred to as WMA) 26.0. A YM copolymer was obtained by carrying out the whole dropwise addition over 2 hours from the addition funnel which mixed 1.2 parts of azobisisobutyronitrile liquid mixture for 2 hours, and making it react for 5 hours. Thereafter, after cooling to room temperature, 13.2 parts of acrylic acid, 0.3 part of triphenylphosphine, and 0.1 part of metoquinone were added, the dropping funnel was removed, the nitrogen inlet was exchanged with an air bubbling device, and stirred while bubbling air. The reaction was carried out for 6 hours to obtain a polyester acrylate having a weight average molecular weight of 17,000. 2 parts of Irgacure 184 were mix | blended with respect to 100 parts of this polyester acrylates, and it was set as the active energy ray hardening type hard coat resin composition of 40% of solid content.

&Lt; Comparative Example 7 &

100 parts of NV ester A-9300-1CL, 5 parts of Irgacure 184, and 145 parts of MEV were mixed, and it was set as the active energy ray resin composition of 40% of solid content.

Comparative Example 8

Examples of the polyfunctional acrylate having flexibility include ε-caprolactone modified dipentaerythritol hexaacrylate; 100 parts of brand name "DPCA-120" (Nihon Kayaku Co., Ltd.), 5 parts of Irgacure 184, and 145 parts of MEB were mixed to obtain an active energy ray resin composition having a solid content of 40%.

Comparative Example 9

15.9 parts of isophorone diisocyanate, polycarbonate diol (number average molecular weight 1000, brand name "Duranol T6001" Asahi Kasei Chemicals) 35.8 parts, methyl isobutyl to a four-necked flask equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen inlet. 40 parts of ketones were added, warmed to 60 degrees while stirring, and warmed for 1 hour, 0.05 parts of dibutyltin diacetate was added and reacted at 80 degrees for 2 hours, and isophorone diisocyanate was added to both ends of the OH group of the polycarbonate diol. The isocyanate groups were introduced into 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, followed by heating to 80 ° C for 5 hours for reaction, and 2-OH group of 2-hydroxyethyl acrylate at the isocyanate terminal. In addition, polycarbonate urethane diacrylate (resin 6) was obtained. After cooling to room temperature, 5 parts of Irgacure 184 and 47 parts of MEV were mixed to obtain an active energy ray resin composition having a solid content of 40%.

The hard coating agent of each Example and the comparative example was apply | coated with the bar coater No. 12 on the back side for the adhesive of the 188 micrometer-thick one side adhesive polyethylene terephthalate film (brand name "Cosmoshine A4100" Toyo Spinning Co., Ltd.), and 80 degree | times, for 1 minute. After drying, ultraviolet light was irradiated with 300 mPa / cm ² to obtain a cured film having a thickness of 5 μm.

The cured film created using the hard coat agent of each Example and the comparative example was evaluated by the pencil hardness test and the scratch resistance test as evaluation of hard coating property. Evaluation of workability evaluated the elongation computed by the tension test which extends a cured film to one direction, and the flexibility. These evaluation results are shown in Tables 2 and 3.

(Pencil hardness test)

Pencil hardness was evaluated based on WIS-K-5600. It was evaluated that the hard coating property was sufficiently satisfied with the hardness of pencil hardness F or more as the outstanding hardness, and the hard coating property was evaluated as the thing below pencil hardness Ｂ.

(Evaluation of scratch resistance)

Using 100 g steel wool, a 100 g / cm ² load was applied to scratch the surface of the cured film, and the presence or absence of a wound was visually checked. If there were no wounds, it had excellent hard coating property, and if there were several wounds, it could be used as a hard coating agent, and if there were many wounds, it was evaluated as an unsuitable result as a hard coating agent.

(Height)

The elongation degree is set in a tensile tester (model number "RTC-1250A" Orientec Co., Ltd.) at a distance of 50 mm between the chuck to cut a cured film into a rectangular shape of 100 mm in length and 7 mm in width, the environment at 25 degrees room temperature, humidity 45% RH. Below, a tensile speed of 10 mm / mN was carried out, and the distance between the chucks was 60 mm (20% elongation), 65 mm (30% elongation), and 70 mm (40% elongation), respectively, to stop the cracks in the cured film. Was visually observed. (Circle) if there was no crack, and if a crack generate | occur | produced, it evaluated as x. The flexibility of the cured film can be evaluated by measuring the elongation of the cured film. When the elongation degree is large, it can be said to be a flexible cured film. For example, since it can flexibly follow the stress of elongation in the molding process of an applied film, the crack of a cured film can be suppressed and it can contribute to workability. .

(Evaluation of Flexibility)

The surface of the cured film was made to face outward, it wound up by the cylinder of (phi) 2mm, and the presence or absence of the crack was visually confirmed. If there was no crack, it was ○. If there was a crack, it was ×.

Claims (8)

It is provided in the thiol terminal of the polyfunctional thiol compound (A) of which polyhydric value calculated by (1) is 100 or more and 200 or less and at least one terminal of the bifunctional (meth) acrylate compound (B). The (meth) acryloyl base to be made by en-thiol reaction (ene-thiol reactivity), and has a multi-functional, characterized in that it has two or more terminal structures represented by the general formula (1) Thio (meth) acrylate resin.
[Number 1]

[Formula 1]

(One)
(Wherein X represents a structure excluding terminal thiol groups of the polyfunctional thiol compound (A). R ₁ and R ₃ each represent hydrogen or a methyl group, and R ₂ represents O or —O—R ₉ —O—. R ₉ is a straight chain of C1~20 (直鎖狀) or branched alkylene group (分岐狀), - (CH 2 CH 2 O) mCH 2 CH 2 -, - (CH 2 CH (CH 3) O _{) mCH 2 CH (CH 3)} -, -CH 2 CH 2 OP = O (OH) OCH 2 CH 2 -, -CH 2 CH (OH) CH 2 - , and the following formulas (1-1) to (1- It is at least one selected from the structure represented by 3), m, p and q represent a positive integer, p + q = 2-6.)

(1-1)

(1-2)

(1-3)
(Meth) which is provided in the thiol terminal of the polyfunctional thiol compound (A) whose X value calculated by (1) is 100 or more and 200 or less, and at least one terminal of the bifunctional (meth) acrylate compound (B) The polyfunctional thio (meth) acrylate resin which has a terminal structure represented by following General formula (2) which the acryloyl group couple | bonded by the en-thiol reaction.
(2)

(2)
(Wherein X represents a structure excluding terminal thiol groups of the polyfunctional thiol compound (A). R ₁ and R ₃ each represent hydrogen or a methyl group, and R ₂ represents O or —O—R ₉ —O—. R ₉ is an alkylene group linear or branched _{C1~20, - (CH 2 CH 2} O) mCH 2 CH 2 -, - (CH 2 CH (CH 3) O) mCH 2 CH (CH 3) -, At least one selected from the structures represented by -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). M, p, and q represent a positive integer, p + q = 2-6.)

(1-1)

(1-2)

(1-3)
3. The method according to claim 1 or 2,
The polyfunctional thiol compound (A) contains at least one kind of polyfunctional thiol compound represented by the following general formula (3)-(7), The polyfunctional thio (meth) acrylate resin characterized by the above-mentioned.
(3)

(In formula, R <_4> is hydrogen or a methyl group and n shows the integer of 1-12.)
[Chemical Formula 4]

(In formula, R <_5> represents hydrogen or a methyl group.)
[Chemical Formula 5]

(In formula, R <_6> represents hydrogen or a methyl group.)
[Chemical Formula 6]

(In formula, R <_7> represents hydrogen or a methyl group.)
(7)

(In formula, R <_8> represents hydrogen or a methyl group.)
The polyfunctional thio (meth) acrylate resin of any one of Claims 1-3, the polyfunctional (meth) acrylate provided with three or more (meth) acryloyl groups, and a photoinitiator are contained, It is characterized by the above-mentioned. Active energy ray-curable hard coating resin composition.
The cured film obtained by hardening | curing by irradiating an active energy ray to the active-energy-ray-curable hard-coating resin composition of Claim 4, The cured film characterized by the above-mentioned.
A plastic film in which the cured film of claim 5 is laminated.
Plastic injection molded article using the plastic film of Claim 6.
The processed product which laminated | stacked the plastic film of Claim 6.