JP6394258B2 - Curable composition, cured product and laminate - Google Patents

Description

  The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition having good elongation at the time of molding and anti-blocking properties, and excellent scratch resistance, hardness and transparency after processing, from the curable composition. And a laminate using the curable composition.

  Generally, plastic products such as polycarbonate (PC) resin, polymethyl methacrylate (PMMA) resin, polyethylene terephthalate (PET) resin, vinyl chloride resin, acetylnitrile-butadiene-styrene (ABS) resin, cellulose acetate, polypropylene (PP) Resins and the like are used for various applications because of their light weight, easy processability, impact resistance, and the like. However, since these plastic products have a low surface hardness, they are easily scratched, making it difficult to use plastic products in fields where wear resistance is required. For this reason, a hard coat material that increases hardness and imparts scratch resistance (scratch resistance) is required for these plastic products. Further, when a hard coat treatment is performed on the surface of these plastic products, the hard coat material is a plastic product (hereinafter, an article in which the hard coat material is to be finally formed may be referred to as a “molded product”). It is not applied directly to the surface, but once applied to the substrate to form a hard coat material coating on the substrate (hereinafter referred to as “transfer sheet”). In addition, a method of transferring a hard coat material from a base material to the surface of a plastic product through processing such as application of a printing layer and an adhesive layer as required is widely used.

  As such a hard coat material, a radical polymerization type curable composition that cures in a short time by irradiation with active energy rays provides a film or a molded product excellent in scratch resistance, chemical resistance, stain resistance, etc. Therefore, it is widely used in various surface processing fields and cast molding applications.

  The method of laminating a hard coat layer on a molded product with such a curable composition includes curing the curable composition with active energy rays and then transferring the cured film to the molded product, and curing with active energy rays. There is a method in which a coating film of the curable composition is formed on the substrate before the transfer, the transfer sheet coating film obtained is transferred to a molded article, and then cured by active energy rays.

  In the former method, since the supplied cured film is previously cured by active energy rays, it has excellent blocking resistance, but there is a problem that the cured film is insufficiently stretched and the moldability is impaired. Further, if the elongation is to be increased, sufficient hardness as a hard coat material cannot be maintained, and it is difficult to satisfy both the moldability and the hardness performance. On the other hand, in the latter method, the cured film precursor is supplied to the surface of the molded product before being cured by active energy rays, so that the moldability is excellent and the hardness after curing is sufficiently increased. It is also possible to satisfy both formability and hardness performance. However, there is a problem that the transfer sheet before curing is likely to be blocked, and there is a need for improvement.

In addition, as the simplest means to improve the anti-blocking property by appropriately crosslinking reaction of a curable composition that is generally cured by active energy rays, ultraviolet rays are irradiated as much as necessary to improve the anti-blocking property. Although curing is performed, as a result of the crosslinking reaction proceeding more than necessary even with a weak UV irradiation amount, it was difficult to ensure sufficient workability (elongation).
That is, it is generally a difficult problem to achieve both anti-blocking properties and processability.

  Patent Document 1 discloses a curable composition containing an acrylic acrylate oligomer and a urethane acrylate oligomer as a curable composition that attempts to achieve both anti-blocking properties and processability. Patent Document 2 discloses a curable composition containing an acrylic acrylate prepolymer and a polyfunctional isocyanate.

JP 2012-102159 A JP 2012-041479 A

  According to the detailed study by the present inventors, the problem that the antiblocking property is insufficient is found in Patent Document 1. On the other hand, Patent Document 2 is a technique for improving the elastic modulus of a coating film by performing a crosslinking reaction with a polyfunctional isocyanate and improving antiblocking properties. However, the isocyanate group of the polyfunctional isocyanate reacts with the organic solvent itself. Therefore, a problem has been found that the types of organic solvents that can be used are limited.

  The present invention has been made in view of the above-mentioned problems of the prior art, and the object of the present invention is to have good elongation at the time of molding, anti-blocking properties, and excellent scratch resistance after processing, hardness, It is in providing the curable composition which has transparency, the hardened | cured material which consists of this curable composition, and the laminated body using this curable composition.

As a result of intensive studies to solve the above problems, the present inventors have identified two types of (meth) acrylic acid ester-based polymers having different amounts of highly reactive acryloyl groups and less reactive methacryloyl groups. It was found that the curable composition contained at a ratio of 1 had good elongation at the time of molding and anti-blocking properties and excellent scratch resistance, hardness and transparency after processing, and reached the present invention.
That is, the gist of the present invention is as follows [1] to [9].

[1] The following component (A) , component (B) and organic solvent are contained, the content of the organic solvent is 10% by weight or more, and the weight ratio of component (A) to component (B) is 5:95. A curable composition that is -95: 5.
Component (A): The weight average molecular weight (Mw _A ) is 1,000 to 500,000, the acryloyl group amount is 2.0 to 5.0 mmol / g, and the methacryloyl group amount is less than 2.0 mmol / g ( (Meth) acrylic acid ester polymer component (B): weight average molecular weight (Mw _B ) is 1,000 to 500,000, methacryloyl group amount is 2.0 to 5.0 mmol / g, acryloyl group amount is 2 (Meth) acrylic acid ester polymer of less than 0.0 mmol / g

[2] The ratio (Mw _A : Mw _B ) of the weight average molecular weight (Mw _A ) of the component ( _A ) and the weight average molecular weight (Mw _B ) of the component ( _B ) is 50: 1 to 1:50, [1] The curable composition according to [1].

[3] The component (A) is obtained by reacting a (meth) acrylic acid ester-based polymer having an epoxy group with a compound having an acryloyl group and a carboxyl group, [1] or [2] The curable composition according to 1.

[4] The component (B) is obtained by reacting a (meth) acrylic acid ester-based polymer having an epoxy group with a compound having a methacryloyl group and a carboxyl group, [1] to [3] The curable composition according to any one of the above.

[5] The organic solvent according to any one of [1] to [4], wherein the organic solvent includes at least one selected from a saturated hydrocarbon solvent, an ester solvent, an ether solvent, an alcohol solvent, and a ketone solvent. Curable composition.

[6] Furthermore, a polymerization initiator is included, and the content thereof is 0.01 to 20 parts by weight with respect to 100 parts by weight as a total of component (A) and component (B). [1] to [5] The curable composition according to any one of the above.

[7] A cured product obtained by irradiating the curable composition according to any one of [1] to [6] with active energy rays.

[8] A laminate having a substrate and a hard coat layer, the hard coat layer being coated with the curable composition according to any one of [1] to [6] on the substrate. A laminate formed by irradiation with active energy rays.

[9] The laminate according to [8], wherein the substrate is a plastic substrate.

  The curable composition of the present invention has good extensibility and antiblocking properties during molding, and has excellent scratch resistance, hardness, and transparency after processing. For this reason, the curable composition, hardened | cured material, and laminated body of this invention can be used suitably for a transfer film use. For example, the present invention can be effectively applied to interior and exterior building materials and various members such as automobiles, home appliances, and information electronic materials. In particular, the cured product obtained from the curable resin composition of the present invention is useful as a decorative film using this as a top coat layer.

It is a graph which shows the relationship between the ultraviolet irradiation amount in Example 3 and Comparative Examples 1 and 2, and the reaction rate of hardening reaction.

  Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is limited to the following description unless it exceeds the gist. is not. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression. In the present invention, when the expression “(meth) acryl” is used, it means one or both of “acryl” and “methacryl”. The same applies to “(meth) acrylate” and “(meth) acryloyl”. In addition, “(poly) propylene glycol” means one or both of “propylene glycol” and “polypropylene glycol”. “(Poly) ethylene glycol” has the same meaning.

(Curable composition)
The curable composition of this invention contains the following component (A) and component (B), and the weight ratio of a component (A) and a component (B) is 5: 95-95: 5.
Component (A): The weight average molecular weight (Mw _A ) is 1,000 to 500,000, the acryloyl group amount is 2.0 to 5.0 mmol / g, and the methacryloyl group amount is less than 2.0 mmol / g ( (Meth) acrylic acid ester polymer (hereinafter may be referred to as “(meth) acrylic acid ester polymer (A)”)
Component (B): The weight average molecular weight (Mw _B ) is 1,000 to 500,000, the methacryloyl group amount is 2.0 to 5.0 mmol / g, and the acryloyl group amount is less than 2.0 mmol / g ( (Meth) acrylic acid ester polymer (hereinafter sometimes referred to as “(meth) acrylic acid ester polymer (B)”)
In the present invention, the “(meth) acrylic acid ester polymer” means a polymer obtained using at least a (meth) acrylic acid ester as a raw material.

  The curable composition of the present invention has excellent elongation and anti-blocking properties at the time of molding, and has excellent scratch resistance and hardness after processing. That is, the curable composition of the present invention has good elongation and antiblocking properties when the active energy ray is set to a low dose, and when the curing reaction is sufficiently advanced with the active energy ray set to a high dose. Has high scratch resistance and hardness. The reason why the curable composition of the present invention has such an effect is that the component (A) and the component (B) each have a relatively reactive acryloyl group and a less reactive methacryloyl group, This is considered to be due to the fact that the degree of progress of the crosslinking reaction can be controlled.

[Component (A)]
The component (A) (meth) acrylate polymer (A) used in the present invention has a weight average molecular weight (Mw _A ) of 1,000 to 500,000 and an acryloyl group amount of 2.0 to 5. There is no particular limitation as long as the amount is 0.0 mmol / g and the amount of methacryloyl group is less than 2.0 mmol / g.

The weight average molecular weight (Mw _A ) of the component (A) (meth) acrylic acid ester polymer (A) is 1,000 or more in order to enhance the antiblocking property, and the (meth) acrylic acid ester polymer In order to prevent gelation of the polymer (A), it is 500,000 or less. From the viewpoint of making these better, the weight average molecular weight (Mw _A ) is preferably 3,000 or more, more preferably 5,000 or more, and further preferably 7,000 or more. Preferably, it is preferably 10,000 or more, on the other hand, preferably 400,000 or less, more preferably 250,000 or less, still more preferably 100,000 or less, and 50,000. It is particularly preferred that The weight average molecular weights (Mw _A ) and (Mw _B ) of the (meth) acrylic acid ester polymer (A) and the (meth) acrylic acid ester polymer (B) described later are GPC (gel permeation chromatography). Can be determined as a conversion value based on polystyrene standards. A specific method for measuring the weight average molecular weight is shown in the Examples below.

  The (meth) acrylic acid ester polymer (A) of the component (A) has an acryloyl group and the acryloyl group amount is 2.0 to 5.0 mmol / g. An amount of acryloyl group of 2.0 mmol / g or more is necessary to improve the scratch resistance and hardness of the cured product obtained when the active energy ray is set at a high dose, and 5 It is necessary to prevent gelation of the curable composition to be 0.0 mmol / g or less. From the viewpoint of making these more favorable, the amount of acryloyl group is preferably 2.2 mmol / g or more, more preferably 2.4 mmol / g or more, while it is 4.8 mmol / g or less. It is preferable that it is 4.6 mmol / g or less.

Moreover, even if the (meth) acrylic acid ester polymer (A) does not have a methacryloyl group or has a methacryloyl group, the amount of the methacryloyl group is less than 2.0 mmol / g.
In other words, the (meth) acrylic acid ester polymer (A) has a highly reactive acryloyl group to increase the progress of the crosslinking reaction, and ensures a sufficient amount of acryloyl group. In order to enhance this function, the amount of methacryloyl group needs to be less than 2.0 mmol / g. From the viewpoint of improving this function, the amount of methacryloyl group is preferably 1.0 mmol / g or less, more preferably 0.5 mmol / g or less, while the lower limit of the amount of methacryloyl group is usually 0 mmol / g, that is, those having no methacryloyl group.

  In addition, the amount of acryloyl groups and the amount of methacryloyl groups of the (meth) acrylic acid ester polymer (A) and the (meth) acrylic acid ester polymer (B) described later are the (meth) acrylic acid ester polymer (A). (B) It is a value calculated from the theoretical amount of the charge on the assumption that all of the charge amounts of the raw material components used in the production of each have reacted. More specifically, for example, in the case of the method [1] in the following (meth) acrylic acid ester polymer (A), preparation of a radical polymerizable monomer having a carbon-carbon unsaturated double bond as a raw material The (meth) acrylic acid ester polymer having an epoxy group was obtained by reacting all the amounts, and the (meth) acrylic acid ester polymer having an epoxy group and a compound having an acryloyl group and a carboxyl group were further obtained. It is a value calculated from the theoretical amount of charging of these raw materials when it is assumed that the reaction has been completed completely with the theoretical amount.

  In the (meth) acrylic acid ester polymer (A) of component (A), the acryloyl group can be introduced as follows.

  For example, a method of producing a (meth) acrylic acid ester-based polymer having an epoxy group and reacting this with a compound having an acryloyl group and a carboxyl group (method [1]), a (meth) acrylic acid ester having a carboxyl group A method of producing a polymer and reacting it with a compound having an acryloyl group and an epoxy group (Method [2]), producing a (meth) acrylic acid ester polymer having a hydroxyl group, and then adding an acryloyl group and a carboxyl A method of reacting a compound having a group (method [3]), a method of producing a (meth) acrylic acid ester-based polymer having a carboxyl group, and reacting a compound having an acryloyl group and a hydroxyl group (method [4]) ), (Meth) acrylic acid ester-based polymer having an isocyanate group, and acrylo A method of reacting a compound having a hydroxyl group and a hydroxyl group (method [5]), a method of producing a (meth) acrylic acid ester-based polymer having a hydroxyl group, and reacting a compound having an acryloyl group and an isocyanate group (method) [6]) and the like. Further, the above methods may be used in combination. Hereinafter, the radical polymerizable monomer having C═C may be referred to as “vinyl monomer”.

  In the said method [1], as a vinyl monomer which has an epoxy group used in order to obtain the (meth) acrylic acid ester-type polymer which has an epoxy group, it represents with following formula (1)-(3), for example. Things. These may be used alone or in combination of two or more.

(Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and p represents an integer of 1 to 8).

(Here, R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴ represents a —CH ₂ O— group or —CH ₂ — group, and R ⁵ represents a hydrogen atom or 1 to 2 carbon atoms. And q represents an integer of 0 to 7.)

(Here, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents an integer of 1 to 8)

In formula (1), preferred as R ¹ and R ² are each independently a hydrogen atom or a methyl group. Specific examples of the monomer represented by the formula (1) include glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate. Among them, glycidyl methacrylate (GMA) is available. From the viewpoint of

In the formula (2), preferred as R ³ and R ⁵ are each independently a hydrogen atom or a methyl group, and preferred as R ⁴ is —CH ₂ O—. Specific examples of the monomer represented by the formula (2) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α -Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether can be exemplified, among which o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether Is preferable from the viewpoint of availability.

In formula (3), R ⁶ is preferably a hydrogen atom or a methyl group. Examples of the monomer represented by the formula (3) include 3,4-epoxycyclohexylmethyl (meth) acrylate. Among them, 3,4-epoxycyclohexylmethyl methacrylate is preferable from the viewpoint of physical properties of the cured product of the curable composition such as hardness.

  In the method [1], examples of the compound having an acryloyl group and a carboxyl group to be reacted with the (meth) acrylic acid ester-based polymer having an epoxy group include acrylic acid, carboxyethyl acrylate, glycerin diacrylate and anhydrous Examples include adducts of succinic acid, adducts of pentaerythritol triacrylate and succinic anhydride, adducts of pentaerythritol triacrylate and phthalic anhydride, and the like. Among these, an adduct of acrylic acid, pentaerythritol triacrylate and succinic anhydride is preferable, and acrylic acid is particularly preferable. In addition, the compound which has an acryloyl group and a carboxyl group may be used individually by 1 type, or may be used in combination of 2 or more type.

  Examples of the vinyl monomer having a carboxyl group used for obtaining the (meth) acrylic acid ester-based polymer having a carboxyl group in the method [2] include (meth) acrylic acid, carboxyethyl (meth) acrylate, Examples include basic acid-modified (meth) acrylate. Among these, (meth) acrylic acid is preferable. These may be used alone or in combination of two or more.

  In the method [2], examples of the compound having an acryloyl group and an epoxy group that are reacted with a (meth) acrylic acid ester-based polymer having a carboxyl group include glycidyl acrylate and 4-hydroxybutyl acrylate glycidyl ether. It is done. Among these, glycidyl acrylate is preferable. These may be used alone or in combination of two or more.

  Examples of the vinyl monomer having a hydroxyl group used to obtain a (meth) acrylic acid ester-based polymer having a hydroxyl group in the method [3] include 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, and the like. Is mentioned. These may be used alone or in combination of two or more.

  In the method [3], as the compound having an acryloyl group and a carboxyl group to be reacted with the (meth) acrylic acid ester-based polymer having a hydroxyl group, the same compounds as those mentioned in the method [1] are used. be able to.

  In the method [4], as the vinyl monomer having a carboxyl group used for obtaining a (meth) acrylic acid ester-based polymer having a carboxyl group, the same compounds as those mentioned in the method [2] are used. be able to.

  In the method [4], examples of the compound having an acryloyl group and a hydroxyl group to be reacted with the (meth) acrylic acid ester-based polymer having a carboxyl group include 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and hydroxypropyl. An acrylate etc. are mentioned. These may be used alone or in combination of two or more.

  In the method [5], examples of the vinyl monomer having an isocyanate used for obtaining a (meth) acrylic acid ester-based polymer having an isocyanate group include isocyanate ethyl (meth) acrylate. These may be used alone or in combination of two or more.

  In the method [5], examples of the compound having an acryloyl group and a hydroxyl group to be reacted with the (meth) acrylic acid ester-based polymer having an isocyanate group include the same compounds as those mentioned in the method [4]. Can be used.

  In the method [6], the vinyl monomer having a hydroxyl group used for obtaining a (meth) acrylic acid ester-based polymer having a hydroxyl group may be the same as the compound mentioned in the method [3]. it can.

  Moreover, in the said method [6], an isocyanate ethyl acrylate etc. are mentioned as a compound which has an acryloyl group and an isocyanate group made to react with the (meth) acrylic acid ester-type polymer which has a hydroxyl group. These may be used alone or in combination of two or more.

  In the following, in the methods [1] to [6], the (meth) acrylic acid ester polymer (A) as the component (A) or the (meth) acrylic acid ester polymer as the component (B) described later. (B) (meth) acrylic acid ester polymer having an epoxy group, (meth) acrylic acid ester polymer having a carboxyl group, (meth) acrylic acid ester polymer having a hydroxyl group, isocyanate group The (meth) acrylic acid ester-based polymer having the above may be referred to as “raw material (meth) acrylic acid ester-based polymer”.

  Among the above-mentioned methods [1] to [6], the reaction is that the acryloyl group in the (meth) acrylic acid ester polymer is the method [1] or [2], particularly the method [1]. Is preferable because it is easy to control. When the component (A) (meth) acrylic acid ester polymer (A) is obtained by the method [1], the acryloyl group is usually an epoxy group of the raw material (meth) acrylic acid ester polymer, an acryloyl group, and It is introduced by ring-opening / addition reaction with a carboxyl group in a compound having a carboxyl group.

  In the method [1], the monomer having an epoxy group used for producing the raw material (meth) acrylate polymer is an acryloyl group out of the total amount of monomers constituting the raw material (meth) acrylate polymer. Is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 90% by weight or more, while the upper limit is not particularly limited, 100% by weight or less.

  In the method [1], the compound having an acryloyl group and a carboxyl group is a carboxyl of a compound having an acryloyl group and a carboxyl group with respect to an epoxy group of a raw material (meth) acrylate polymer having an epoxy group. The proportion of the group is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, particularly preferably 50 to 110 mol%, and the reaction proceeds without excess or deficiency. It is preferable from the viewpoint of reducing the amount of residue.

  In the method [1], in addition to the vinyl monomer having an epoxy group described above, the (meth) acrylic acid ester listed below is used as the raw material for the raw material (meth) acrylic acid ester polymer of the component (A). And other vinyl monomers can be used. The polymerization reaction of these raw materials is usually radical polymerization and can be carried out under known conditions.

  Examples of (meth) acrylic acid esters other than monomers having an epoxy group that can be used as raw materials include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid. Butyl, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) propylene glycol (meth) Acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, methoxytetramethylene glycol (meth) acrylate, octoxy (poly) ethylene glycol (meth) acrylate, octoxy (poly) propylene Recall (meth) acrylate, octoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, octoxytetramethylene glycol (meth) acrylate, lauroxy (poly) ethylene glycol (meth) acrylate, stearoxy (poly) ethylene glycol ( And (meth) acrylate. These may use only 1 type or may use 2 or more types.

  Other vinyl monomers that can be used as raw materials include ethyl (meth) acrylamide, n-butyl (meth) acrylamide, i-butyl (meth) acrylamide, t-butyl (meth) acrylamide, and N-hydroxyethyl (meth). Acrylamides such as acrylamide, N-hydroxypropyl (meth) acrylamide, N, N-dihydroxyethyl (meth) acrylamide; and styrene monomers such as styrene, p-chlorostyrene, and p-bromostyrene. These may use only 1 type or may use 2 or more types.

  The raw material (meth) acrylic acid ester polymer can be produced using the above-mentioned raw material vinyl monomer and using a known radical polymerization reaction. The radical polymerization reaction can usually be carried out in an organic solvent in the presence of a radical polymerization initiator.

  Examples of the organic solvent that can be used for the radical polymerization reaction include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ethylene glycol dimethyl ether and propylene. Examples include ether solvents such as glycol monomethyl ether; ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene. These organic solvents may be used alone or in combination of two or more.

  As the radical polymerization initiator, known radical polymerization initiators can be used. For example, organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2′-azobisbutyronitrile Azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is usually used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of raw material vinyl monomers.

  In the production of the raw material (meth) acrylate polymer, it is preferable to use a chain transfer agent because the control of the weight average molecular weight is easy.

  As the chain transfer agent, known ones can be used, for example, butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, 2 -Octyl mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercapto Propionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, octameric acid 2-mercaptoethyl ester, 1,8-dimerca -3,6-dioxaoctane, decane trithiol, dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, Examples include thiol-based compounds such as 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, and 2-mercaptoethanesulfonic acid. These may be used alone or in combination of two or more.

  The amount of the chain transfer agent used is preferably 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, and still more preferably 1 to 100 parts by weight of the total amount of vinyl monomers used as a raw material. 0.0 to 15 parts by weight.

  The reaction time for the radical polymerization reaction is usually 1 to 20 hours, preferably 3 to 12 hours. Moreover, reaction temperature is 40-120 degreeC normally, Preferably it is 50-100 degreeC.

  In order to produce a raw material (meth) acrylate polymer having a predetermined weight average molecular weight so that the weight average molecular weight of the component (A) (meth) acrylate polymer (A) falls within the above range. For example, a method of controlling polymerization conditions such as polymerization temperature, amount of polymerization initiator, amount of chain transfer agent, vinyl monomer concentration in the reaction system, and method of adding vinyl monomer can be employed.

  In order to react a raw material (meth) acrylate polymer with a compound having an acryloyl group and a carboxyl group, the raw material (meth) acrylate polymer obtained as described above is reacted with an acryloyl group and a carboxyl. In the presence of one or more of a catalyst such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride, triethylamine, and the like, usually at 80 to 150 ° C., preferably 90 to 130. The reaction may usually be performed at 3 ° C. for about 3 to 9 hours. Here, the catalyst is used at a ratio of about 0.5 to 3 parts by weight with respect to 100 parts by weight in total of the raw material (meth) acrylic acid ester polymer and the compound such as the compound having an acryloyl group and a carboxyl group. Is preferred. This reaction may be continued after the polymerization reaction of the raw material (meth) acrylate polymer, and after once separating the raw material (meth) acrylate polymer from the reaction system, the acryloyl group and the carboxyl group You may carry out by adding compounds, such as a compound which has this.

  The curable composition of this invention may contain only 1 type of the (meth) acrylic acid ester type polymer (A) obtained as mentioned above as a component (A), and 2 or more types may be included. May be included.

[Component (B)]
The component (B) (meth) acrylate polymer (B) used in the present invention has a weight average molecular weight (Mw _A ) of 1,000 to 500,000 and a methacryloyl group amount of 2.0 to 5. There is no particular limitation as long as it is 0.0 mmol / g and the amount of acryloyl group is less than 2.0 mmol / g.

The weight average molecular weight (Mw _B ) of the component (B) (meth) acrylic acid ester polymer (B) is 1,000 or more in order to enhance the antiblocking property, and the (meth) acrylic acid ester polymer In order to prevent gelation of the polymer (B), it is 500,000 or less. From the viewpoint of making these more favorable, the weight average molecular weight (Mw _B ) is preferably 3,000 or more, more preferably 5,000 or more, and further preferably 7,000 or more. On the other hand, it is preferably 400,000 or less, more preferably 300,000 or less, and further preferably 250,000 or less.

  The component (B) (meth) acrylic acid ester polymer (B) has a methacryloyl group, and the amount of the methacryloyl group is 2.0 to 5.0 mmol / g. It is necessary for the methacryloyl group amount to be 2.0 mmol / g or more in order to improve the elongation and antiblocking property of the cured product obtained when the active energy ray is low, and 5 It is necessary to prevent gelation of the curable composition to be 0.0 mmol / g or less. From the viewpoint of making these more favorable, the amount of methacryloyl group is preferably 2.2 mmol / g or more, more preferably 2.4 mmol / g or more, while it is 4.8 mmol / g or less. It is preferable that it is 4.6 mmol / g or less.

Moreover, even if the (meth) acrylic acid ester polymer (B) does not have an acryloyl group or has an acryloyl group, the amount of the acryloyl group is less than 2.0 mmol / g.
That is, the (meth) acrylic acid ester polymer (B) has a low reactivity methacryloyl group to reduce the progress of the crosslinking reaction, and ensures a sufficient amount of methacryloyl group. In order to enhance this function, the amount of acryloyl group needs to be less than 2.0 mmol / g. From the viewpoint of improving this function, the amount of acryloyl groups is preferably 1.0 mmol / g or less, more preferably 0.5 mmol / g or less, while the lower limit of the amount of acryloyl groups is usually 0 mmol / g, that is, those having no acryloyl group.

  In the (meth) acrylic acid ester polymer (B) of the component (B), the methacryloyl group is introduced in the same manner as the acryloyl group of the (meth) acrylic acid ester polymer (A) of the component (A). Can do. That is, the (meth) acrylic acid ester polymer (B) is obtained by using a compound having a methacryloyl group in place of the acryloyl group in the method for producing the (meth) acrylic acid ester polymer (A). It can be produced in the same manner by reacting with a raw material (meth) acrylic acid ester polymer.

  In the production of the (meth) acrylic acid ester polymer (B), in the method [1], [3], as the compound having a methacryloyl group and a carboxyl group to be reacted with the raw material (meth) acrylic acid ester polymer. 1 or 2 of, for example, methacrylic acid, carboxyethyl methacrylate, an adduct of glycerin dimethacrylate and succinic anhydride, an adduct of pentaerythritol trimethacrylate and succinic anhydride, an adduct of pentaerythritol trimethacrylate and phthalic anhydride, or the like More than species. Among these, an adduct of methacrylic acid, pentaerythritol trimethacrylate and succinic anhydride is preferable, and methacrylic acid is particularly preferable. In the methods [4] and [5], examples of the compound having a methacryloyl group and a hydroxyl group to be reacted with the raw material (meth) acrylic acid ester polymer include 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, and hydroxypropyl. 1 type, or 2 or more types, such as a methacrylate, are mentioned.

In the method [2], as the compound having a methacryloyl group and an epoxy group to be reacted with the raw material (meth) acrylic acid ester polymer, for example, glycidyl methacrylate, 4-hydroxybutyl methacrylate diglycidyl ether or the like Two or more types can be mentioned. Among these, glycidyl methacrylate is preferable.
In the method [6], examples of the compound having a methacryloyl group and an isocyanate group to be reacted with the raw material (meth) acrylate polymer include one or more of isocyanate ethyl methacrylate and the like.

  Similarly to the (meth) acrylate polymer (A), the methacryloyl group in the (meth) acrylate polymer is the method [1] or [ 2], in particular, the method [1] is preferable because the reaction can be easily controlled. When the component (B) (meth) acrylate polymer (B) is obtained by the method [1], the methacryloyl group is usually an epoxy group of the raw material (meth) acrylate polymer, a methacryloyl group, and It is introduced by ring-opening / addition reaction with a carboxyl group in a compound having a carboxyl group.

  The curable composition of this invention may contain only 1 type of the (meth) acrylic acid ester type polymer (B) obtained as mentioned above as a component (B), and 2 or more types may be included. May be included.

[Content ratio of component (A) and component (B)]
The curable composition of this invention contains a component (A) and a component (B) in the ratio of 5: 95-95: 5 by weight ratio. When the content ratio of the component (A) is larger than this range and the content ratio of the component (B) is small, the present invention is based on the combined use of the highly reactive component (A) and the less reactive component (B). The effect of controlling the degree of progress of the crosslinking reaction is effectively obtained, that is, it has good extensibility and anti-blocking properties at the time of molding processing, and has excellent scratch resistance, hardness and transparency after processing. I can't. In order to make this effect even better, the content ratio of the component (A) and the component (B) is preferably 90:10 to 10:90 by weight ratio, and 85:15 to 15:85. It is more preferable that the ratio is 80:20 to 20:80.

The ratio (Mw _A : Mw _B ) between the weight average molecular weight (Mw _A ) of the component ( _A ) and the weight average molecular weight (Mw _B ) of the component (B) contained in the curable composition of the present invention is as follows. In order to more effectively obtain the effect obtained by using together, it is preferably 50: 1 to 1:50. The ratio (Mw _A : Mw _B ) of the weight average molecular weight (Mw _A ) of the component ( _A ) and the weight average molecular weight (Mw _B ) of the component (B) is out of the above range, and the component (A) and the component ( When the molecular weight difference from B) is within the above range, the compatibility of the curable composition tends to be good, and the transparency of the cured product tends to be good. In this respect, (Mw _A : Mw _B ) is more preferably 1:40 to 40: 1, further preferably 1:30 to 30: 1, and 1:20 to 20: 1. Is particularly preferred.

[Organic solvent]
The curable composition of the present invention preferably contains an organic solvent. It is preferable that the curable composition of this invention is prepared by 5-95 weight% of solid content concentration by including an organic solvent. The solid content concentration of the curable composition is preferably 5% by weight or more in order to prevent an unintended curing reaction (such as gelation) of the curable composition, and it is preferably 95% by weight or less. From the viewpoint of From these viewpoints, the solid content concentration is more preferably 10% by weight or more, further preferably 20% by weight or more, more preferably 90% by weight or less, and further preferably 85% by weight or less. Particularly preferably, it is 80% by weight or less. In the present invention, “solid content” means a component excluding the solvent, and includes not only a solid component but also a semi-solid or viscous liquid material.

  It does not specifically limit as an organic solvent, In consideration of the kind of base material used when forming a component (A) and a component (B), a hard-coat layer, the coating method to a base material, etc. It can be selected appropriately. Specific examples of the organic solvent include, for example, n-hexane, n-heptane, n-octane, n-decane, n-dodecane, 2,3-dimethylhexane, 2-methylheptane, 2-methylhexane, and 3-methyl. Saturated hydrocarbon solvents such as hexane and cyclohexane; aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, Ether solvents such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetole; ethyl acetate, Ester solvents such as butyl acid, isopropyl acetate and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; methanol, ethanol and propanol And alcohol solvents such as isopropanol and butanol; halogen solvents such as dichloromethane and chloroform.

  The curable composition of the present invention is not limited by the type of organic solvent that can be used, as in the case of using a polyfunctional isocyanate, and various organic solvents can be used. Of these, at least one selected from saturated hydrocarbon solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents is preferably used.

[Polymerization initiator]
The curable composition of the present invention preferably contains a polymerization initiator in order to improve curability by active energy rays.

  As the polymerization initiator, a photopolymerization initiator is preferable. For example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [ 4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) -butanone-1,2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2,4 , 6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. It is. These polymerization initiators may be used alone or in a combination of two or more.

  The content of the polymerization initiator in the curable composition of the present invention is preferably 0.01 parts by weight or more with respect to a total of 100 parts by weight of the component (A) and the component (B) from the viewpoint of enhancing curability. More preferably, it is 0.05 parts by weight or more, and still more preferably 0.1 parts by weight or more. Moreover, from the viewpoint of the stability of the curable composition, the content of the polymerization initiator is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 5 parts by weight or less.

[Inorganic particles]
The curable composition of the present invention may further contain inorganic particles having an average primary particle size of 1 μm or less. By containing such inorganic particles, it is possible to obtain a curable composition capable of forming a hard coat layer having further excellent hardness and anti-blocking properties.

  Examples of inorganic particles include silica (including organosilica sol), alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide) / Tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, antimony oxide and the like. Among these, silica is preferable. Moreover, the inorganic particle mentioned above may use only 1 type, and may be used in combination of 2 or more type.

  The average primary particle diameter of the inorganic particles is 1 μm or less, preferably 800 nm or less, more preferably 500 nm or less, still more preferably 300 nm or less, and particularly preferably 100 nm or less. The lower limit of the average primary particle diameter of the inorganic particles is not particularly limited, but is usually 5 nm or more, preferably 10 nm or more. It is preferable for the average primary particle size to be not more than the above upper limit because precipitation due to the weight of the particles hardly occurs and the storage stability of the coating liquid of the curable composition tends to be good.

  On the other hand, since the movement in the coating liquid of the curable composition of the inorganic particles whose average primary particle diameter is in the above range is governed by thermal diffusion rather than sedimentation by gravity, the inorganic particles are in the coating liquid of the curable composition. It is possible to disperse stably, and when the hard coat layer is formed, it is effectively present on the surface. Moreover, there exists a tendency for an optical characteristic to become favorable, so that the average primary particle diameter of an inorganic particle is small.

In addition, the average primary particle diameter of the inorganic particle in this invention calculates | requires the specific surface area measured value (based on JISZ8830) by a BET adsorption method, and is a value calculated | required as a conversion value from the following formula | equation.
[Average primary particle diameter (nm)] = 6,000 / [[specific surface area (m ² / g)]
× [Density (g / cm ³ )]]

  When the curable composition of the present invention contains the inorganic particles as described above, the content thereof is 0.05 parts by weight or more with respect to 100 parts by weight in total of the component (A) and the component (B). Preferably, it is 0.5 parts by weight or more, more preferably 0.7 parts by weight or more, and particularly preferably 1 part by weight or more. Further, it is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, and still more preferably 60 parts by weight or less with respect to 100 parts by weight of the total of component (A) and component (B). 40 parts by weight or less is particularly preferable. It is preferable that the content of the inorganic particles is not less than the above lower limit value, since the effect of using the inorganic particles can be sufficiently obtained, and is preferably not more than the above upper limit value from the viewpoint of transparency.

  In addition, the inorganic particle may be mix | blended with the curable composition of this invention as an inorganic particle surface-modified with the component (A) and / or the component (B) in the point which improves antiblocking property and hardness. . In order to produce inorganic particles surface-modified with the component (A) and / or the component (B), for example, the component (A) and / or the component (B) and the inorganic particles are combined with an acid, a base, acetylacetone aluminum or the like. And a method of reacting at 25 to 120 ° C. for about 1 to 24 hours in the presence of the silane coupling reaction catalyst.

[Other ingredients]
The curable composition of this invention may contain other components other than a component (A), a component (B), an organic solvent, a polymerization initiator, and an inorganic particle in the range which does not inhibit the effect of this invention. Other components include UV absorbers, hindered amine light stabilizers, fillers, silane coupling agents, reactive diluents, antistatic agents, organic pigments, slip agents, dispersants, thixotropic agents (thickeners). ), Antifoaming agents, antioxidants and the like.

[Method for producing curable composition]
Although the manufacturing method of the curable composition of this invention is not restrict | limited in particular, For example, it can obtain by mixing a component (A) and (B) and another component suitably as needed. When mixing each component, it is preferable to mix uniformly with a disperser, a stirrer, or the like.

[Hardened product / Laminate]
The cured product of the present invention can be obtained by curing the curable composition of the present invention by irradiating it with active energy rays. In particular, by applying and curing the curable composition of the present invention on a substrate or the like, a laminated body formed by forming a cured layer made of the curable composition of the present invention on the substrate is obtained. it can. Moreover, a hard coat film (hard coat layer) can be obtained by apply | coating the curable composition of this invention on a base material etc. in this way, and making it harden | cure to a film form. Moreover, the film lamination formed by apply | coating the curable composition of this invention on another resin film as a base material, making it harden | cure, and shape | molding a hard-coat film, and laminating | stacking a hard-coat film on another resin film The body is obtained. In the present invention, “application” is used as a concept including what is generally called “coating”.

  As a base material used for said laminated body, inorganic materials, such as organic materials, such as a plastic base material; a metal base material, a glass base material, are mentioned. Examples of plastic substrates include various synthetic resins such as acrylonitrile-butadiene-styrene copolymer (ABS) resin, polycarbonate (PC) resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polymethyl methacrylate (PMMA). ) Resin, polystyrene (PS) resin, polyolefin resin and the like. The metal substrate is not particularly limited. For example, a steel plate such as a hot-rolled plate or a cold-rolled plate, a hot-dip galvanized steel plate, an electrogalvanized steel plate, tinplate, tin-free steel, various other types of plating or alloy-plated steel plate And metal plates such as stainless steel plates and aluminum plates. Furthermore, these may be subjected to various surface treatments such as phosphate treatment, chromate treatment, organic phosphate treatment, organic chromate treatment, heavy metal substitution treatment such as nickel. As a glass substrate, in addition to normal glass, glass subjected to various chemical treatments (for example, Corning Gorilla Glass (registered trademark), Asahi Glass Dragon Trail (registered trademark), etc.) and multicomponent glass. May be used. The curable composition of the present invention is suitable for plastic substrates and glass substrates, and particularly suitable for plastic substrates.

  The hard coat layer formed on the substrate can be formed, for example, by applying (coating) the curable composition of the present invention on the substrate and irradiating it with active energy rays. Examples of the method for coating (coating) the curable composition of the present invention on a substrate include, for example, a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a Mayer bar coating method, a die coating method, and a spray coating. Law. The form of the cured product of the present invention is not particularly limited. Usually, a cured product obtained by irradiating and curing an active energy ray on a substrate is a cured film (cured) on at least a part of one side of the substrate. Film).

  Active energy rays that can be used in curing the curable composition of the present invention include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. Among these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoints of curability and prevention of resin deterioration.

When the curable composition of the present invention is cured by ultraviolet irradiation, various ultraviolet irradiation apparatuses can be used, and a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED-UV lamp, or the like is used as the light source. Can do. Irradiation amount of the ultraviolet (in mJ / cm ²⁾ is usually 10~10,000mJ / cm ^2, in view of flexibility, such as the curing of the curable composition of the present invention, a cured product (cured film) from preferably 100~5,000mJ / cm ^2, more preferably 200~3,000mJ / cm ^2.

  Moreover, when hardening the curable composition of this invention by electron beam irradiation, various electron beam irradiation apparatuses can be used. The irradiation amount (Mrad) of the electron beam is usually 0.5 to 20 Mrad, and preferably 1 from the viewpoints of curability of the curable composition of the present invention, flexibility of the cured product, prevention of damage to the substrate, and the like. ~ 15 Mrad.

In addition, after applying (coating) the curable composition of the present invention onto a substrate, it is a semi-cured film that has sufficient anti-blocking properties and excellent extensibility when irradiated with weak active energy rays. The irradiation amount of the active energy ray in the case of the above varies depending on the ratio of the component (A) and the component (B) in the curable composition, but usually 1 to 50 mJ / cm ^{2 in the} case of ultraviolet rays. It is preferable that it is 5-20 mJ / cm < ² >.

[Use]
The curable composition of the present invention has good stretchability and antiblocking properties during molding, and has excellent scratch resistance, hardness and transparency after processing, that is, after curing. It can be suitably used as a curable composition for a film. For example, the present invention can be effectively applied to interior and exterior building materials and various members such as automobiles, home appliances, and information electronic materials. In particular, the cured product obtained from the curable composition of the present invention is useful as a decorative film using this as a top coat layer.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

In addition, the weight average molecular weight of the (meth) acrylic acid ester polymer (“A-1”, “B-1”, “B-2”) produced in the following production examples was measured by the GPC method under the following conditions. It is the value.
Equipment: “HLC-8120GPC” manufactured by Tosoh Corporation
Column: “TSKgel Super H3000 + H4000” manufactured by Tosoh Corporation
+ H6000 "
Detector: Differential refractive index detector (RI detector / built-in)
Solvent: Tetrahydrofuran Temperature: 40 ° C
Flow rate: 0.5 ml / min Injection volume: 10 μL
Concentration: 0.2% by weight
Calibration sample: Monodisperse polystyrene Calibration method: Polystyrene conversion

[Production example]
[Production Example 1]
In a flask equipped with a thermometer, stirrer and reflux condenser, 155.1 g propylene glycol monomethyl ether, 98.0 g glycidyl methacrylate, 1.0 g methyl methacrylate, 1.0 g ethyl acrylate, 1.9 g mercaptopropyltrimethoxysilane, and 1.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted at 65 ° C. for 3 hours. Thereafter, 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours, and then 122.8 g of propylene glycol monomethyl ether and 0.52 g of p-methoxyphenol were added and 100 ° C. Until heated. Next, 50.7 g of acrylic acid and 3.05 g of triphenylphosphine were added and reacted at 110 ° C. for 6 hours, thereby having an acryloyl group and a methoxysilyl group, and a weight average molecular weight (Mw) of 20,100. A (meth) acrylic acid ester polymer (A) having an acryloyl group amount of 4.5 mmol / g was obtained (solid content: 30% by weight). Hereinafter, this (meth) acrylic acid ester polymer (A) is referred to as “A-1”. The physical properties of “A-1” are shown in Table 1.

[Production Example 2]
In a flask equipped with a thermometer, stirrer and reflux condenser, 155.1 g propylene glycol monomethyl ether, 98.0 g glycidyl methacrylate, 1.0 g methyl methacrylate, 1.0 g ethyl acrylate, 1.9 g mercaptopropyltrimethoxysilane, and 1.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted at 65 ° C. for 3 hours. Thereafter, 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours, and then 236.3 g of propylene glycol monomethyl ether and 0.56 g of p-methoxyphenol were added and 100 ° C. Until heated. Next, 60.5 g of methacrylic acid and 3.25 g of triphenylphosphine were added and reacted at 110 ° C. for 6 hours, thereby having a methacryloyl group and a methoxysilyl group, and having a weight average molecular weight (Mw) of 9,000. A (meth) acrylic acid ester polymer (B) having a methacryloyl group amount of 4.1 mmol / g was obtained (solid content: 30% by weight). Hereinafter, this (meth) acrylic acid ester polymer (B) is referred to as “B-1”. The physical properties of “B-1” are shown in Table 1.

[Production Example 3]
In a flask equipped with a thermometer, stirrer and reflux condenser, 81.1 g propylene glycol monomethyl ether, 58.1 g methacrylic acid, 4.0 g methyl methacrylate and 2,2′-azobis (2,4-dimethylvaleronitrile) 0 .62 g was added and reacted at 65 ° C. for 3 hours. Thereafter, 0.32 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours, and then 262.1 g of propylene glycol monomethyl ether and 0.53 g of p-methoxyphenol were added and 100 ° C. Until heated. Next, 96.0 g of glycidyl methacrylate and 1.58 g of tetrabutylammonium bromide were added and reacted at 110 ° C. for 6 hours, thereby having a methacryloyl group and a weight average molecular weight (Mw) of 210,000. 4.3 mmol / g of (meth) acrylic acid ester polymer (B) was obtained (solid content: 30% by weight). Hereinafter, this (meth) acrylic acid ester polymer (B) is referred to as “B-2”. The physical properties of “B-2” are shown in Table 1.

〔Evaluation method〕
[Evaluation of coating film or semi-cured film]
<Elongation>
The coated film or semi-cured film is peeled off from the PET film, cut to a width of 10 mm, and pulled using a tensile tester (manufactured by Imada, vertical electric measuring stand MX2-500N-FA and FA-Plus) at a temperature of 140 ° C. A tensile test was performed under the conditions of a speed of 40 mm / min and a distance between chucks of 40 mm to measure the elongation at break.

<Anti-blocking property>
A PET film on which a coating film or a semi-cured film was formed and a PET film on which no film was formed were prepared one by one, and these were superposed at 40 ° C. with the coating film or the semi-cured film inside. Then, after applying a load of 400 g / cm ² for 24 hours, the degree of sticking (blocking) of the coating film or semi-cured film to the other PET film was examined by visual observation and evaluated according to the following criteria.
○: The area where sticking occurred was less than 20% of the area of the laminated coating film or semi-cured film.
X: The area where sticking occurred was 20% or more in the area of the laminated coating film or semi-cured film.

[Evaluation of cured film]
<Transparency (total light transmittance, haze)>
The total light transmittance (T _t (%)) of the hard coat film (PET film on which a cured film is formed) is the incident light intensity (T ₀ ) to the hard coat film and the total transmitted light intensity (T ₁ ) and measured by the following formula. The total light transmittance was measured using a haze meter (manufactured by Murakami Color Research Laboratory: HM-65W). The total light transmittance is preferably 85.0% or more.
Tt (%) = (T ₁ / T ₀ ) × 100

The haze of the hard coat film was measured using a haze meter (Murakami Color Research Laboratory) and calculated from the following formula in accordance with JIS K-7136 (2000). The haze is preferably 1.0% or less.
H (%) = (T _d / T _t ) × 100
H: Haze (cloudiness value) (%)
T _d : Diffuse transmittance (%)
T _t : Total light transmittance (%)

<Hardness (pencil hardness)>
About the obtained cured film, pencil hardness was measured according to JIS-K5600.

<Abrasion resistance>
The obtained cured film was observed for scratches on the cured film when steel wool (Bonster # 000) was rubbed 10 times under a load of 500 g / cm ² and evaluated according to the following criteria.
○: scars are hardly seen Δ: some scratches are seen ×: many scratches are seen

[Comprehensive evaluation]
<Anti-blocking property>
The evaluation result of the anti-blocking property of the semi-cured film (ultraviolet ray irradiation amount: 15 mJ / cm ² ) was used.

<Elongation>
When the elongation of the coating film (ultraviolet ray irradiation amount 0 mJ / cm ² ) is 180% or more and the semi-cured film (ultraviolet ray irradiation amount 15 mJ / cm ² ) is 50% or more, the elongation rate is “good”. Those not satisfying the above elongation were regarded as poor elongation “x”.

<Abrasion resistance>
The evaluation result of the scratch resistance of the cured film was used.

[Reaction rate of curing reaction]
The reaction rate before and after the curing reaction is based on the reaction rate of the (meth) acryloyl group, and the peak height ratio ((meta) of the specific wave number observed when FT-IR (Fourier transform infrared spectroscopy) is measured. )) (Peak height derived from acryloyl group) / (peak height derived from ester bond)) was converted by comparing uncured film, semi-cured film and cured film. However, regarding the “peak height derived from the (meth) acryloyl group”, the infrared absorption seen at 780 to 830 cm ⁻¹ was regarded as the baseline, and the height was determined.
In addition, the peak used for calculation of the reaction rate is observed in the following wave number range.
Peak derived from (meth) acryloyl group: 802 to 814 cm ⁻¹
Peak derived from ester bond: 1650-1800 cm ⁻¹
Moreover, the measurement conditions of FT-IR (Speckin 100 manufactured by Perkin Elmer) of the measuring instrument are as follows.
・ Measurement condition integration count: 4 times Resolution: 4 cm ^-1
・ Reaction rate calculation method (Reaction rate of curing reaction)
= [1-((height) peak height ratio observed in cured film) / (peak height ratio observed in uncured film)] × 100

[Examples and Comparative Examples]
[Example 1]
<Manufacture of curable composition>
In a four-necked flask, as a component (A), a solid content concentration of 30% by weight (meth) acrylic acid ester polymer “A-1” is 25.0 parts by weight as a solid content, and as a component (B) is a solid 75.0 parts by weight of (meth) acrylic acid ester polymer “B-1” having a partial concentration of 30% by weight as solid content and 1-hydroxy-cyclohexyl-phenyl-ketone (“Irgacure” manufactured by BASF as a polymerization initiator) (Registered trademark) 184 ") 2.5 parts by weight was added to obtain a curable composition having a solid content of 30% by weight.

<Manufacture of semi-cured film>
The curable composition was applied to an easily molded polyethylene terephthalate (PET) film (thickness: 100 μm) having a thickness of 100 μm with a bar coater (# 14) so that the film thickness after drying was 4 to 5 μm. After application, a drying time of 1 minute was provided at 80 ° C. to remove the solvent contained in the coating solution. Using this dried coating film, the elongation and antiblocking property were evaluated by the above methods.
Subsequently, the coated film was irradiated with ultraviolet rays at 15 mJ / cm ² (35 mW / cm ² ) using an ultraviolet irradiation device (UCI-6NAH-4) manufactured by GS Yuasa Corporation to obtain a semi-cured film. Using the obtained semi-cured film, the elongation and antiblocking property were evaluated by the above methods.
The results are shown in Table-2.

<Manufacture of cured film>
The cured composition was applied onto an A4 size polyethylene terephthalate (PET) film (thickness: 125 μm) so as to have a film thickness of 4 to 5 μm after drying, and dried at 80 ° C. for 1 minute. Using a high-pressure mercury lamp with an output density of 120 W as a light source, an integrated light quantity of 500 mJ / cm ² (450 mW / cm ² ) using an ultraviolet irradiation device (EYE UV METER UVPF-A1, PD365) manufactured by Eyegraphic Co., Ltd. at a position 15 cm below the light source. The cured composition on the PET film was cured by irradiating ultraviolet rays so that a cured film was obtained. Using the obtained cured film, transparency, hardness and scratch resistance were evaluated by the above methods.
The results are shown in Table-2.

[Examples 2 to 4 and Comparative Examples 1 and 2]
A curable composition was obtained in the same manner as in Example 1 except that the composition of the component (A) and the component (B) in the curable composition was changed to the composition shown in Table-2. Furthermore, using each of the obtained curable compositions, a dried coating film, a semi-cured film and a cured film were produced in the same manner as in Example 1, and each of the above evaluations was performed. These results are shown in Table-2.

From the above results, according to the present invention, by using the component (A) and the component (B) in a predetermined ratio, it has good extensibility and anti-blocking property before curing. It can be seen that a cured film having excellent scratch resistance, hardness, and transparency can be obtained after curing. In particular, in Examples 1 and 2 where less reactive component (A) was used than in Component (B), semi-curing was higher than in Examples 3 and 4 where the same amount of Component (A) and Component (B) was used. The elongation rate of the film is large.
On the other hand, in Comparative Example 1 using only the component (A), the crosslinking reaction at a low UV irradiation amount proceeds too much, so that the elongation percentage of the semi-cured film is low. On the contrary, in Comparative Example 2 using only the component (B), since the progress of the crosslinking reaction at a low UV irradiation amount is slow, the elongation of the semi-cured film is large, but the anti-blocking property is poor, and the cured film The scratch resistance is also inferior.

Incidentally, the reaction when the respective Examples 3 and 15mJ a relationship (amount of ultraviolet irradiation of the reaction rate of the curing reaction with UV irradiation amount in Comparative Example ^{1,2 / cm 2, 50mJ / cm} 2, 500mJ / cm 2 (Rate) is shown in a graph in FIG. From FIG. 1, in Comparative Example 1, the reaction rate exceeds 30% when the ultraviolet irradiation amount is 50 mJ / cm ^2, and in Comparative Example 2, the reaction rate is even when the ultraviolet irradiation amount is 500 mJ / cm ^2. Is less than 60%. Meanwhile Example 3 the reaction rate is suppressed below 20% when the amount of ultraviolet irradiation and 50 mJ / cm ^2, also the reaction rate when the amount of ultraviolet irradiation and 500 mJ / cm ² is 80% or more It has become. That is, it can be seen that the progress of the curing reaction can be controlled by adjusting the ratio of the component (A) to the component (B).

Claims (9)

The composition contains the following component (A) , component (B) and organic solvent , the organic solvent content is 10% by weight or more, and the weight ratio of component (A) to component (B) is from 5:95 to 95: A curable composition which is 5.
Component (A): The weight average molecular weight (Mw _A ) is 1,000 to 500,000, the acryloyl group amount is 2.0 to 5.0 mmol / g, and the methacryloyl group amount is less than 2.0 mmol / g ( (Meth) acrylic acid ester polymer component (B): weight average molecular weight (Mw _B ) is 1,000 to 500,000, methacryloyl group amount is 2.0 to 5.0 mmol / g, acryloyl group amount is 2 (Meth) acrylic acid ester polymer of less than 0.0 mmol / g The ratio (Mw _A : Mw _B ) of the weight average molecular weight (Mw _A ) of the component ( _A ) and the weight average molecular weight (Mw _B ) of the component ( _B ) is 50: 1 to 1:50. The curable composition as described.   The curable composition according to claim 1 or 2, wherein the component (A) is obtained by reacting a (meth) acrylic acid ester-based polymer having an epoxy group with a compound having an acryloyl group and a carboxyl group. Composition.   The component (B) is obtained by reacting a (meth) acrylic acid ester-based polymer having an epoxy group with a compound having a methacryloyl group and a carboxyl group. The curable composition according to 1. The curable property according to any one of claims 1 to 4, wherein the organic solvent contains at least one selected from a saturated hydrocarbon solvent, an ester solvent, an ether solvent, an alcohol solvent, and a ketone solvent. Composition.   Furthermore, it contains a polymerization initiator, and the content is 0.01-20 weight part with respect to a total of 100 weight part of a component (A) and a component (B). The curable composition according to 1.   Hardened | cured material formed by irradiating an active energy ray to the curable composition of any one of Claims 1 thru | or 6.   It is a laminated body which has a base material and a hard-coat layer, and this hard-coat layer apply | coats the curable composition of any one of Claims 1 thru | or 6 on this base material, and this is an active energy ray. A layered product formed by irradiating.   The laminate according to claim 8, wherein the substrate is a plastic substrate.

Images