JP2015227437A - Active energy ray-curable resin composition and laminate and molding using cured film of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin which has high hardness and flexibility and allows restoration of flaws or making flaws inconspicuous by excellent resilience even when flaws occur and a molding and a film suitable for surface protection applications of a variety of substrates.SOLUTION: A resin (X) has a resilience (x) and an indentation elastic modulus of values specified in (i) and (ii), respectively, measured by a nano-indentation method, and shows a pencil hardness of H or higher. (i) The resilience (x) of the resin calculated by expression (1) is 70-100%. (ii) The indentation elastic modulus is 10-2,000 MPa.

Description

  The present invention relates to an active energy ray-curable resin composition, a laminate and a molded body using the cured film. The cured film of the resin composition of the present invention is excellent in flexibility and flaw resilience, and exhibits high pencil hardness, and thus can be suitably used for surface protection of various substrates.

  Industrial products such as automobile interior parts such as dashboards, automobile exterior parts such as tail lamp covers, casings and various parts such as mobile phones and personal computers, optical members such as lenses and window glass, and home appliances such as microwave ovens, When transported or used, the surface is scratched, resulting in problems such as deterioration of transparency and loss of appearance.

  In order to solve these problems, it is common to apply a hard coating with a high hardness on the surface of the product for the purpose of imparting scratch resistance, chemical resistance and the like. However, with a general hard coat that exhibits high hardness, it is possible to impart scratch resistance and chemical resistance to the surface of the product, but once scratched, the scratch remains semi-permanently. There is a problem.

In order to solve this problem, a technique for restoring a scratch using a resin having high elasticity for the outermost layer has been proposed (for example, Patent Document 1). However, in the metal plate using the paint proposed here, a high temperature is required to cure the paint, and the high hardness due to the metal plate may be expressed. It is assumed that it is difficult to use it for a molded product.
In addition, a hard coat technique that achieves both formability and flexibility has been proposed (for example, Patent Document 2). In the patent document, there is a description about the elongation and hardness of the hard coat coating film, but no examination has been made on the restoration of the coating film, and the scratch may remain when scratched.

WO2010 / 134617 JP 2009-184284 A

  An object of the present invention is to provide a resin that has a high hardness and is flexible and capable of restoring or making it inconspicuous by its excellent restoring force even when scratched. Moreover, it aims at providing the molded object and film which can be used conveniently for the surface protection use of various base materials.

ここで、復元率（ｘ）は上記測定条件で測定され、算出に用いたＬｓ，Ｌｅ，Ｌｍａｘはそれぞれ、Ｌｓ：荷重を加え始めた際の初期の押込み深さ、Ｌｅ：除荷後、更に２５秒間保持した後の押込み深さ、Ｌｍａｘ：５ｍＮで１０秒保持した後の最も深く圧子が押し込まれた際の押込み深さ、である。
（ｉｉ）・・・押込み弾性率が１０ＭＰａ以上２０００ＭＰａ以下。

＜２＞側鎖に活性エネルギー線により硬化可能な官能基を有する熱可塑性樹脂（Ａ）を含有する、＜１＞に記載の樹脂（Ｘ）を製造するための樹脂組成物。

＜３＞熱可塑性樹脂（Ａ）が、以下の単量体成分（ａ）を重合して得られ且つ以下の（ｉｉｉ）を示す重合体に、ラジカル重合性の不飽和基とカルボキシル基を有する単量体を反応させて得られる重合体である＜２＞に記載の樹脂組成物。
単量体成分（ａ）
・エポキシ基を有する（メタ）アクリレート（ａ−１）：５〜７０質量％
・（ａ−１）以外の（メタ）アクリレート（ａ−２）：９５〜３０質量％
・（ａ−１）及び（ａ−２）と共重合可能な単量体（ａ−３）：０〜３０質量％
（ｉｉｉ）・・・ガラス転移温度（Ｔｇ）が０℃以下。
ここで、Ｔｇは、ＦＯＸの式から算出した値をいう。

＜４＞無機微粒子（Ｂ）を更に含有する＜２＞または＜３＞に記載の樹脂組成物。

＜５＞多官能単量体（Ｃ）を更に含有する＜４＞に記載の樹脂組成物。

＜６＞多官能単量体（Ｃ）が、１分子内に２個以上のラジカル重合性官能基及びポリアルキレングリコール構造を有する多官能単量体である＜５＞に記載の樹脂組成物。

＜７＞多官能チオール化合物（Ｄ）を更に含有する＜２＞〜＜６＞のいずれか一項に記載の樹脂組成物。

＜８＞＜２＞〜＜７＞のいずれか一項に記載の樹脂組成物を活性エネルギー線により硬化してなる樹脂（Ｘ）。

＜９＞＜７＞に記載の樹脂組成物を熱硬化した後、さらに活性エネルギー線により硬化してなる樹脂（Ｘ）。

＜１０＞＜１＞に記載の樹脂（Ｘ）または＜８＞または＜９＞に記載の硬化された樹脂（Ｘ）の層を、基材の少なくとも片方の面に有する積層体。

＜１１＞基材がフィルム形状である＜１０＞に記載の積層体。

＜１２＞＜７＞に記載の樹脂組成物の層を有する積層体を加熱し、樹脂組成物の層を熱硬化した後、成形を行い、さらに該樹脂組成物の層を活性エネルギー線で硬化して得られる樹脂（Ｘ）の層を有する成形体。 It has been found that the above object is achieved by using a resin having a specific restoration rate and indentation elastic modulus and having a certain hardness.
That is, the present invention provides the following.
<1> Resin recovery rate (x) and indentation elastic modulus measured under the following measurement conditions by the nanoindentation method show the values described in (i) and (ii) below, and the pencil hardness is H or higher Resin (X).
Measurement conditions A load is applied to the surface of the resin while gradually increasing the load to the Vickers indenter at 5 mN / 5 seconds. The load is unloaded while being held, and after unloading, hold for 25 seconds.
(I) The resin restoration rate (x) calculated from the following formula (1) is 70% or more and 100% or less.

Here, the restoration rate (x) is measured under the above measurement conditions, and Ls, Le, and Lmax used for the calculation are Ls: initial indentation depth when the load is started, Le: after unloading, and further, The indentation depth after being held for 25 seconds, Lmax: the indentation depth when the indenter was most deeply pushed in after being held at 5 mN for 10 seconds.
(Ii) The indentation elastic modulus is 10 MPa or more and 2000 MPa or less.

<2> A resin composition for producing the resin (X) according to <1>, which contains a thermoplastic resin (A) having a functional group curable with active energy rays in the side chain.

<3> The thermoplastic resin (A) is obtained by polymerizing the following monomer component (a) and has a radical polymerizable unsaturated group and a carboxyl group in a polymer having the following (iii): <2> The resin composition according to <2>, which is a polymer obtained by reacting monomers.
Monomer component (a)
-(Meth) acrylate having an epoxy group (a-1): 5 to 70% by mass
-(Meth) acrylates other than (a-1) (a-2): 95 to 30% by mass
-Monomer (a-3) copolymerizable with (a-1) and (a-2): 0 to 30% by mass
(Iii) Glass transition temperature (Tg) is 0 ° C. or lower.
Here, Tg is a value calculated from the FOX equation.

<4> The resin composition according to <2> or <3>, further containing inorganic fine particles (B).

<5> The resin composition according to <4>, further containing a polyfunctional monomer (C).

<6> The resin composition according to <5>, wherein the polyfunctional monomer (C) is a polyfunctional monomer having two or more radical polymerizable functional groups and a polyalkylene glycol structure in one molecule.

<7> The resin composition according to any one of <2> to <6>, further containing a polyfunctional thiol compound (D).

<8> Resin (X) obtained by curing the resin composition according to any one of <2> to <7> with active energy rays.

<9> Resin (X) obtained by thermosetting the resin composition according to <7> and further curing with active energy rays.

<10> A laminate having the layer of the resin (X) according to <1> or the cured resin (X) according to <8> or <9> on at least one surface of the substrate.

The laminated body as described in <10> whose <11> base material is a film shape.

<12> The laminate having the resin composition layer according to <7> is heated, the resin composition layer is thermally cured, and then molded, and the resin composition layer is further cured with active energy rays. The molded object which has a layer of resin (X) obtained by this.

  According to the present invention, it is possible to provide a resin that has a high hardness and is flexible and capable of restoring or making the scratch inconspicuous by its excellent restoring force even when it is scratched. Moreover, since the molded object and film using the resin have the said characteristic, they can be used conveniently for the surface protection use of various base materials.

  Hereinafter, although the aspect of this invention is demonstrated in detail, the range of this invention is not restrained by these description and can change suitably in the range which does not impair the meaning of this invention except the following illustration.

<Resin (X)>
Resin (X) used in the present invention exhibits the following restoration ratio (x) and indentation elastic modulus (i) and (ii) measured by the nanoindentation method under the following measurement conditions, and the pencil hardness is H: It is resin which shows the above.
Measurement conditions A load was applied to the surface of the resin while gradually increasing the load on the Vickers indenter under the condition of 5 mN / 5 seconds. The load is unloaded while decreasing, and after unloading, hold for another 25 seconds.

ここで、復元率（ｘ）は上記測定条件で測定され、算出に用いたＬｓ，Ｌｅ，Ｌｍａｘはそれぞれ、Ｌｓ：荷重を加え始めた際の初期の押込み深さ、Ｌｅ：除荷後、更に２５秒間保持した後の押込み深さ、Ｌｍａｘ：５ｍＮで１０秒保持した後の最も深く圧子が押し込まれた際の押込み深さ、である。 (I) The resin restoration rate (x) calculated from the following formula (1) is 70% or more and 100% or less.

Here, the restoration rate (x) is measured under the above measurement conditions, and Ls, Le, and Lmax used for the calculation are Ls: initial indentation depth when the load is started, Le: after unloading, and further, The indentation depth after being held for 25 seconds, Lmax: the indentation depth when the indenter was most deeply pushed in after being held at 5 mN for 10 seconds.

In addition, although measurement by a nanoindentation method can be performed using a well-known apparatus, the following conditions are used in this specification.
Apparatus: Micro hardness tester Fischer scope HM2000
(Fischer Instruments)
Indenter: Vickers indenter (four-sided diamond cone)
Test atmosphere: temperature 23 ° C, humidity 50%
Here, the restoration rate (x) is a value that does not depend on the thickness of the resin (X). However, when the resin (X) is too thin, a sufficient indentation depth cannot be ensured. It is preferable to be within the range described in the section “Thickness of X)>.

  The restoration rate (x) described in the present invention is a value calculated from the above equation (1) under the measurement conditions. When the restoration rate (x) is 70% or more, even when the resin (X) is scratched, it can be recovered to such an extent that the scratch is not noticeable. More preferably, it is 75% or more, More preferably, it is 80% or more.

(Ii) The indentation elastic modulus is 10 MPa or more and 2000 MPa or less.
The indentation elastic modulus described in the present invention is a value calculated based on the ISO14577 standard in the measurement conditions and the measurement apparatus. If the indentation elastic modulus is in the range of 10 MPa or more and 2000 MPa or less, it is possible to ensure sufficient flexibility for the restoration of the resin (X). More preferably, they are 20 MPa or more and 1800 MPa or less, More preferably, they are 30 MPa or more and 1600 MPa or less.

The type of resin used for bringing the restoration rate (x) and the indentation elastic modulus within the above ranges is not particularly limited, and may be appropriately selected from resins such as polyester resin, epoxy resin, urethane resin, acrylic resin, and silicone resin. It can be selected and used. Moreover, these can also be used together.
The resin used may be a thermoplastic resin, or a thermosetting resin or an active energy ray curable resin that crosslinks by applying active energy rays such as ultraviolet rays and electron beams.

In the case of using a curable resin, an active energy ray curable resin is used from the viewpoint of the reaction rate when obtaining the resin (X) and the need to consider the heat resistance of the substrate when curing the resin. It is preferable.
Among these, it is preferable to use the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain from the viewpoint of easy design of the resin (X) obtained, weather resistance and transparency.
As the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain, a radical polymerizable unsaturated group is added to the polymer of the monomer component (a) described later which is the thermoplastic resin (A). The polymer which introduce | transduced is mentioned.

  In order to achieve both indentation elastic modulus and restoration rate (x), the Tg of the polymer of the monomer component (a) is preferably 0 ° C. or less. By setting the Tg of the polymer of the monomer component (a) to 0 ° C. or less, the resin (X) containing the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain is cured. In this case, the flexibility of the resin (X) can be maintained, and the indentation elastic modulus can be easily set in the range of 10 MPa to 2000 MPa. Tg is more preferably −10 ° C. or lower, and further preferably −20 ° C. or lower.

Further, in order to achieve both the recovery rate (x) and the indentation elastic modulus of the resin (X), the radical polymerization property of the side chain of the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain is not observed. As the amount of the saturated group, the double bond equivalent (the amount of resin per 1 mol of unsaturated groups) is preferably 10 to 5,000 g / mol in terms of a calculated value.
By making the double bond equivalent within the range of 10 to 5,000 g / mol, the molecular weight between the crosslinking points of the resin (X) containing the thermoplastic resin (A) is lengthened, and the flexibility is maintained. In addition, it is possible to restore the scratch by elastic recovery.
The double bond equivalent is more preferably 50 to 4,500 g / mol, and still more preferably 100 to 4,000 g / mol.
In addition, the calculation method of a double bond equivalent is mentioned later.

Moreover, it is preferable that the Martens hardness of resin (X) calculated based on the ISO14577 standard in the measurement conditions and the measurement apparatus is in the range of 10 to 200 N / mm ² . If the Martens hardness is 10 N / mm ² or more, the resin (X) can be suppressed to be too soft and the pencil hardness can be suppressed, and by setting it to 200 N / mm ² or less, both flexibility and pencil hardness can be achieved. Is possible. More preferably, it is in the range of 15 to 170 N / mm ² , more preferably 20 to 140 N / mm ² .

<Pencil hardness of resin (X)>
Further, when the resin (X) has a pencil hardness of H or more, the resin is soft and the wound is restored, but the occurrence of the scratch itself can be suppressed. More preferably, it is 2H or more, More preferably, it is 3H or more.
In order to make the pencil hardness of the resin (X) H or more, it is more preferable to contain inorganic fine particles (B) described later. The inorganic fine particles (B) are not particularly limited, but colloidal silica, alumina, titanium oxide, tin oxide, foreign element doped tin oxide (ATO, etc.), indium oxide, foreign element doped indium oxide (ITO, etc.), cadmium oxide. And antimony oxide, which can be appropriately selected and used. Two or more kinds can be used in combination. Among these, colloidal silica is preferably used from the viewpoint of availability and variety.
As the inorganic fine particles (B), inorganic fine particles whose surface is previously treated with a silane compound described later may be used. When the surface-treated inorganic fine particles are used, it is preferable that the storage stability of the resin composition for obtaining the resin (X) is further improved.

<Other components that can be added to the resin (X)>
In order to achieve both flexibility and hardness, it is preferable to use a resin composition containing a polyfunctional monomer (C) described later when the resin (X) is produced. Moreover, in order to achieve further flexibility and hardness, a polyfunctional thiol compound (D) having two or more thiol groups in one molecule described later can be used.
In addition, in the resin (X), an antioxidant, a thermal stabilizer, a light stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, a filler, a matting agent, a processing aid, Various additives such as impact aids, antibacterial agents, antifungal agents, foaming agents, mold release agents, colorants, UV absorbers, sensitizers, leveling agents, anti-repellent agents, thermoplastic polymers, etc. it can.

  Examples of the antioxidant include hindered phenol-based heat stabilizers, sulfur-based heat stabilizers, and hydrazine-based heat stabilizers. Examples of the plasticizer include phthalic acid esters, phosphoric acid esters, fatty acid esters, aliphatic dibasic acid esters, oxybenzoic acid esters, epoxy compounds, and polyesters. Examples of the lubricant include fatty acid esters, fatty acids, metal soaps, fatty acid amides, higher alcohols and paraffins.

  As the ultraviolet absorber, both an organic ultraviolet absorber and an inorganic ultraviolet absorber can be used. Examples of organic ultraviolet absorbers include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, benzoate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and triazine ultraviolet absorbers. Examples of the inorganic ultraviolet absorber include inorganic compounds such as fine particle zinc oxide, cerium oxide, and titanium oxide having a particle diameter of 0.2 μm or less. These may be used alone or in combination of two or more.

  In addition, when using an ultraviolet absorber, the absorption wavelength region of an ultraviolet absorber may overlap with the absorption wavelength region of a photopolymerization initiator (E) described later. In that case, since the curability of the photocurable resin composition, the weather resistance and abrasion resistance of the cured product of the photocurable resin composition may be lowered, the absorption wavelength region of the UV absorber and photopolymerization It is preferable that the absorption wavelength regions of the initiator (E) do not overlap. Among the above-mentioned ultraviolet absorbers, organic ultraviolet absorbers are preferred from the viewpoint of the transparency of the cured product of the photocurable resin composition.

  Examples of the hindered amine light stabilizer include a compound having a piperidine ring in which a plurality of substituents having a steric hindrance action are bonded to two carbon atoms adjacent to each other in the chemical structure. Examples of the substituent exhibiting such steric hindrance include a methyl group. A known compound can be used as the hindered amine light stabilizer, and is not particularly limited. Examples thereof include a compound having a 2,2,6,6-tetramethyl-4-piperidyl group and a compound having a 1,2,2,6,6-pentamethyl-4-piperidyl group. Examples of commercially available products include Uvinul (trademark) 5050H, Uvinul (trademark) 4050FF, Tinuvin (trademark) 622LD, Tinuvin (trademark) 622SF, Tinuvin (trademark) 144, Tinuvin (trademark) PA144, Tinuvin (trademark) 765, and Tinuvin. (Trademark) 770DF, Tinuvin (trademark) 123, Tinuvin (trademark) 292, Sanol (trademark) LS-2626 (trade name, manufactured by BASF Japan Ltd.), ADK STAB (trademark) LA-52, LA-57, LA -63P, LA-68, LA-81, LA-82, LA-87 (above trade names, manufactured by ADEKA Corporation) and the like. These may be used alone or in combination of two or more.

As addition amount of these additives, 0-15 mass parts is preferable with respect to 100 mass parts of resin components which comprise resin (X), 0-10 mass parts is more preferable, and 0-5 mass parts is still more preferable.
Examples of the method of blending the additive include the same method as in the case of the inorganic fine particles (B) described later.

<Thickness of resin (X)>
The resin (X) may be a single-layer film-like or sheet-like molded body formed only from the resin (X), and is provided as a laminate having the resin (X) layer on at least one surface of the substrate. You can also
When providing as a single-layer film-like or sheet-like molded product formed only from the resin (X), it is within the range of 15 to 300 μm from the viewpoint of the handleability of the molded product and the cost of the molded product obtained. More preferably, it is 20-250 micrometers, More preferably, it is 25-200 micrometers.
When providing as a laminated body which has the layer of resin (X) in the at least one surface of a base material, it is preferable to make thickness of the layer of resin (X) into the range of 1-50 micrometers. More preferably, it is 2-40 micrometers, More preferably, it is 3-30 micrometers. By setting the thickness of the resin (X) layer within the range of 1 to 50 μm, it is possible to reflect the characteristics of the elastic coating film having both flexibility and hardness on the surface of the substrate.

<Thermoplastic resin (A) having a functional group curable by active energy rays in the side chain>
As the resin used for producing the resin (X) of the present invention, it is preferable to use a thermoplastic resin (A) having a functional group curable by active energy rays in the side chain. By using the thermoplastic resin (A), when the cured resin (X) is scratched, sufficient flexibility and restoring force are provided to restore or make the scratch inconspicuous. Is possible.
As the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain, for example, a polymer in which a radically polymerizable unsaturated group is introduced into the polymer of the monomer component (a) described later is used. Can be mentioned.

  Examples of the monomer used for the monomer component (a) include N-methylolacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Monomers having a hydroxyl group such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, monomers having a carboxyl group such as (meth) acrylic acid and acryloyloxyethyl monosuccinate, glycidyl (meth) acrylate, 3 , 4-epoxycyclohexylmethyl (meth) acrylate, monomers having an epoxy group such as 4-hydroxybutyl acrylate glycidyl ether, 2-aziridinylethyl (meth) acrylate, aziridinyl such as allyl 2-aziridinylpropionate Monomer with group Monomers having amino groups such as (meth) acrylamide, diacetone acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and sulfo groups such as 2-acrylamido-2-methylpropanesulfonic acid Monomers, adducts of radically polymerizable monomers having diisocyanate and active hydrogen such as equimolar adducts of 2,4-toluene diisocyanate and 2-hydroxyethyl acrylate, 2-isocyanate ethyl (meth) acrylate, etc. Examples include monomers having an isocyanate group. These may be used alone or in combination of two or more.

In order to adjust the glass transition temperature (Tg) of the polymer obtained by polymerizing these monomers, or to adjust the physical properties of the obtained resin, other monomers copolymerizable with these monomers are used. The body can also be used.
Examples of other copolymerizable monomers include (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and isobornyl (meth) acrylate, N- Examples thereof include imide derivatives such as phenylmaleimide, cyclohexylmaleimide and N-butylmaleimide, olefinic monomers such as butadiene, and aromatic vinyl compounds such as styrene and α-methylstyrene. These may be used alone or in combination of two or more.

Moreover, as a monomer used for a monomer component (a), it is represented by the following monomer components (a-1)-(a-3), and the obtained polymer Is preferably a monomer showing the following (iii).
Monomer component (a)
(Meth) acrylate having epoxy group (a-1) 5 to 70% by mass
(Meth) acrylates other than (a-1) (a-2) 95-30% by mass
Other monomers (a-3) copolymerizable with (a-1) and (a-2) 0 to 30% by mass (iii)... Glass transition temperature (Tg) is 0 ° C. or lower.
Here, Tg is a value calculated from the FOX equation.

As (meth) acrylate (a-1) which has an epoxy group, the thing similar to the monomer which has the epoxy group mentioned above can be used. That is, monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 4-hydroxybutyl acrylate glycidyl ether can be used.
Especially, it is preferable to use the compound represented by following formula (2) from a viewpoint of obtaining resin which shows low Tg, and providing a softness | flexibility to resin.

In General Formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear or branched alkylene group having 2 to 10 carbon atoms.

  As a specific example of the commercial item of the said compound, 4-hydroxybutyl acrylate glycidyl ether (For example, Nippon Kasei Co., Ltd. make, brand name: 4HBAGE) is mentioned, for example. As content of the (meth) acrylate (a-1) which has an epoxy group, it is preferable to set it as 5-70 mass%. By having the content within the range of 5 to 70% by mass, the obtained polymer has a functional group curable by active energy rays in the side chain obtained by addition reaction of a monomer having a hydroxyl group or a carboxyl group. The thermoplastic resin (A) is preferable because both flexibility and flaw resilience can be achieved. More preferably, it is 10-60 mass%, More preferably, it is 15-50 mass%.

The (meth) acrylate (a-2) other than (a-1) is not particularly limited as long as it is other than (a-1). Examples include alkyl (meth) acrylates, alkenyl (meth) acrylates, alkynyl (meth) acrylates, and aryl (meth) acrylates. The alkyl moiety may be further substituted with a functional group such as a hydroxyl group, a carboxyl group, an aziridinyl group, an amino group, a sulfo group, or an isocyanate group. A functional group that does not cause an addition reaction with the epoxy group is preferable.
More preferably, the alkyl moiety is a linear, branched or cyclic alkyl having 1 to 10 carbon atoms. The alkenyl moiety is preferably a linear, branched or cyclic alkenyl having 2 to 10 carbon atoms. The alkynyl moiety is preferably a linear, branched or cyclic alkenyl having 3 to 10 carbon atoms. The aryl moiety is preferably an aryl group having 6 to 12 carbon atoms.
Moreover, it can select suitably from (meth) acrylate mentioned above by the monomer component (a), and can use.
Among these, alkyl acrylates are preferably used because it is easy to obtain a resin having a low Tg, it is easy to impart flexibility to the resin, and no addition reaction to the epoxy group occurs.

  As the monomer (a-3) copolymerizable with (a-1) and (a-2), any monomer other than (a-1) and (a-2) can be used. The monomer component (a) can be appropriately selected and used from the monomers described above. Moreover, the macromonomer mentioned later can also be used as a monomer.

As a polymerization initiator used when obtaining the polymer of the component which consists of said monomer component (a) or (a-1)-(a-3), a well-known thing can be used. Although the polymerization initiator is not particularly limited, azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) ), 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), etc .; benzoyl peroxide, cumene hydroperoxide, t-butylhydro Examples include peroxides such as peroxides. These may be used alone or in combination of two or more.
The polymerization initiator is preferably used in an amount of about 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the monomer. From the monomer component (a) or (a-1) to (a-3) Examples of the component polymerization method include a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

Furthermore, the FOX of the polymer obtained by polymerizing the monomer (a-3) copolymerizable with (a-1), (a-2), (a-1) and (a-2) The Tg calculated from the equation is preferably 0 ° C. or lower. By setting Tg to 0 ° C. or lower, flexibility can be imparted to the resin (X) containing the thermoplastic resin (A) having a functional group curable with active energy rays in the side chain. More preferably, it is -10 degrees C or less, More preferably, it is -20 degrees C or less.
Further, as described above, when using a macromonomer described later, Tg calculated only from a monomer other than the macromonomer was used as a reference.

  The monomer (a-3) copolymerizable with (a-1), (a-2), (a-1) and (a-2) in the monomer component (a) is as described above. If Tg of the polymer obtained will be 0 degrees C or less in content, it will not restrict | limit, It can select from the monomer mentioned above suitably and can use.

Further, a macromonomer having a mass average molecular weight within a range of 1,000 to 500,000 having a radical polymerizable functional group at at least one terminal (also referred to as one terminal or both terminals) can also be used. The type of the macromonomer is not particularly limited, but it is preferable to use a (meth) acrylic macromonomer from the viewpoint of transparency, weather resistance, and adhesion to the substrate. In order to improve the scratch resistance, a silicone-based macromonomer may be used as necessary. Furthermore, (meth) acrylic macromonomers, silicone macromonomers, and other macromonomers can be used in combination.
These macromonomers also constitute the components (a-1) to (a-3) of the monomer component (a) described above depending on the type of the repeating unit and the terminal radical polymerizable functional group.

  The mass average molecular weight of the (meth) acrylic macromonomer is more preferably 2,000 to 200,000, and still more preferably 3,000 to 100,000. As such a macromonomer, ELVACITE (Lucite International) series can be suitably used.

The thermoplastic resin (A) having a functional group curable with active energy rays in the side chain can be produced by the following method.
For example, a radically polymerizable unsaturated group is introduced into the polymer of the monomer component (a) by the following method, and a thermoplastic resin (A) having a functional group curable with active energy rays in the side chain is obtained. Can do.
For example, in the case of a homopolymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group or a sulfo group is subjected to a condensation reaction, or a monomer having an epoxy group, an aziridinyl group or an isocyanate group Alternatively, an equimolar adduct of a diisocyanate compound and a hydroxyl group-containing acrylate monomer can be subjected to an addition reaction.
In the case of a homopolymer or copolymer having at least one functional group selected from monomers having a carboxyl group or a sulfo group, a monomer having a hydroxyl group can be subjected to a condensation reaction.
In the case of a homopolymer or copolymer of a monomer having a carboxyl group, an equimolar addition of an epoxy group, an aziridinyl group, a monomer having an isocyanate group or a diisocyanate compound and a hydroxyl group-containing acrylate monomer The product can be subjected to an addition reaction.
In the case of a homopolymer or copolymer having at least one functional group selected from monomers having an epoxy group, an isocyanate group or an aziridinyl group, a monomer having a hydroxyl group or a carboxyl group is subjected to an addition reaction. Can do.

These reactions are preferably performed while adding a small amount of a polymerization inhibitor such as hydroquinone and sending dry air.
When the monomer component (a) using the (meth) acrylate (a-1) having an epoxy group is used, addition of a monomer having a radical polymerizable unsaturated group and a hydroxyl group or a carboxyl group It is preferable to use a reaction.

Further, as another method for introducing a radically polymerizable unsaturated group into the polymer of the monomer component (a), for example, using a solution in which the polymer of the monomer component (a) is dissolved in an organic solvent. And a method in which a monomer having a radical polymerizable unsaturated group and a hydroxyl group or a carboxyl group is subjected to an addition reaction in the presence of a catalyst.
There is no restriction | limiting in particular as a catalyst used for addition reaction, A well-known thing can be used. For example, phosphines such as triphenylphosphine and tricyclohexylphosphine; quaternary ammonium salts such as tetramethylammonium chloride, trimethylbenzylammonium chloride and tetramethylammonium bromide; amines such as trimethylamine, triethylamine and tributylamine; 2-methylimidazole And imidazoles such as dibutyltin dilaurate and the like.
Among them, it is preferable to use a phosphine such as triphenylphosphine from the viewpoint of easy availability and low coloration of the obtained resin composition.
As the monomer having a radical polymerizable unsaturated group and a hydroxyl group or a carboxyl group, it is more preferable to use a monomer having a carboxyl group from the viewpoint of high reactivity with an epoxy group.

Specific examples of the monomer having a radical polymerizable unsaturated group and a carboxyl group include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and ω-carboxy-polycaprolactone mono. Examples include acrylate, monohydroxyethyl acrylate phthalate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
Specific examples of commercially available products include, for example, acrylic acid (manufactured by Mitsubishi Chemical Corporation), β-carboxyethyl acrylate (manufactured by Daicel Ornex Co., Ltd.), Aronix M5300 (ω-carboxy-polycaprolactone monoacrylate, Toa Gosei) And Acryester PA (monohydroxyethyl methacrylate phthalate, manufactured by Mitsubishi Rayon Co., Ltd.).
These may be used alone or in combination of two or more.
Moreover, it is preferable to use acrylic acid and methacrylic acid from the viewpoint of easy availability and high reactivity.

  The amount of radically polymerizable unsaturated groups in the side chain of the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain is the double bond equivalent (the amount of resin per 1 mol of unsaturated groups). A calculated value of 10 to 5,000 g / mol increases the molecular weight between the crosslinking points of the resin (X) containing the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain. However, it is preferable because the scratches can be restored by elastic recovery while maintaining flexibility. The double bond equivalent is more preferably 50 to 4,500 g / mol, and still more preferably 100 to 4,000 g / mol. As described above, by introducing a plurality of radically polymerizable unsaturated groups involved in crosslinking, it is possible to efficiently restore both the flexibility and the damage caused by the elastic recovery. In addition, the calculation method of a double bond equivalent is mentioned later.

  The mass average molecular weight (Mw) of the thermoplastic resin (A) having a functional group curable with active energy rays in the side chain is preferably 1,000 to 2,500,000. More preferably, it is 3,000-1,000,000, More preferably, it is 5,000-500,000. By setting the mass average molecular weight to 1,000 to 2,500,000, the viscosity of the solution of the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain is adjusted to an appropriate viscosity for coating. It is preferable because it can be maintained.

<Inorganic fine particles (B)>
The resin (X) of the present invention can contain inorganic fine particles (B) as necessary. By containing the inorganic fine particles (B), it is possible to impart hardness to the resulting resin (X).
The material of the inorganic fine particles (B) is not particularly limited, but colloidal silica, alumina, titanium oxide, tin oxide, foreign element doped tin oxide (ATO, etc.), indium oxide, foreign element doped indium oxide (ITO, etc.), Examples thereof include cadmium oxide and antimony oxide, which can be appropriately selected from these. Two or more kinds can be used in combination. Among these, colloidal silica is preferably used from the viewpoint of availability and variety.

The particle diameter of the inorganic fine particles (B) is preferably 500 nm or less from the viewpoint of the transparency of the obtained resin. 300 nm or less is more preferable, and 100 nm or less is still more preferable. Moreover, as a lower limit of the particle diameter of inorganic fine particles (B), 1 nm or more is preferable.
In the resin composition for producing the resin (X), colloidal silica can be used in the form of a normal aqueous dispersion or in a form dispersed in an organic solvent. However, in order to disperse uniformly and stably in the resin composition (A), it is preferable to use colloidal silica dispersed in an organic solvent.

  Examples of the organic solvent include methanol, isopropyl alcohol, n-butanol, ethylene glycol, xylene / butanol, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, and toluene. These can be appropriately selected and used as necessary. Two or more kinds can be used in combination.

  Examples of colloidal silica dispersed in an organic solvent include methanol silica sol, isopropyl alcohol silica sol IPA-ST, n-butanol silica sol NBA-ST, ethylene glycol silica sol EG-ST, xylene / butanol silica sol XBA-ST, ethyl cellosolve Silica sol ETC-ST, Butyl cellosolve silica sol BTC-ST, Dimethylformamide silica sol DBF-ST, Dimethylacetamide silica sol DMAC-ST, Methyl ethyl ketone silica sol MEK-ST, Methyl isobutyl ketone silica sol MIBK-ST ). These can be appropriately selected and used as necessary. Two or more kinds can be used in combination.

  The added amount of the inorganic fine particles (B) is preferably 5 to 400 parts by mass in terms of solid content of the inorganic fine particles with respect to 100 parts by mass of the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain. More preferably, it is 10-300 mass parts, More preferably, it is 15-200 mass parts. By making the addition amount of the inorganic fine particles (B) 5 parts by mass or more, an effect of improving the hardness of the obtained resin is recognized. On the other hand, it is preferable for the amount of inorganic fine particles (B) to be 400 parts by mass or less because the storage stability of the resin composition is not impaired.

  In addition, as the inorganic fine particles (B), inorganic fine particles whose surface is previously treated with a silane compound represented by the following formula (I) may be used. When the surface-treated inorganic fine particles are used, it is preferable that the storage stability of the resin composition for obtaining the resin (X) is further improved.

SiR ⁴ _a R ⁵ _b (OR ⁶ ) _c (I)
(In said formula (I), R < ⁴ > and R < ⁵ > represents the C1-C10 hydrocarbon group which may have an ether bond, an ester bond, an epoxy bond, or a carbon-carbon double bond, respectively. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have an ether bond, an ester bond, an epoxy bond or a carbon-carbon double bond. 3 is an integer of 3, and c is an integer of 1 to 4 that satisfies 4-ab.

Among the silane compounds represented by the formula (I), silane compounds represented by the following formulas (II) to (VII) are more preferable.
SiR ⁷ _a R ⁸ _b (OR ⁹ ) _c (II)
SiR ⁷ _n (OCH ₂ CH ₂ OCO (R ¹⁰ ) C═CH ₂ ) _4-n (III)
CH ₂ ═C (R ¹⁰ ) COO (CH ₂ ) _p SiR ¹¹ _n (OR ⁹ ) _3-n (IV)
CH ₂ = CHSiR ¹¹ _n (OR ⁹ ) _3-n (V)
HS (CH ₂ ) _p SiR ¹¹ _n (OR ⁹ ) _3-n (VI)

（前記式（ＩＩ）から（ＶＩＩ）中、Ｒ⁷及びＲ⁸は、それぞれ、エーテル結合、エステル結合又はエポキシ結合を有していてもよい炭素数１〜１０の炭化水素基を表す。Ｒ⁹は水素原子又は炭素数１〜１０の炭化水素基を表す。Ｒ¹⁰は水素原子又はメチル基を表す。Ｒ¹¹は炭素数１〜３のアルキル基又はフェニル基を表す。ａ及びｂは、それぞれ、０〜３の整数であり、ｃは４−ａ−ｂを満足する１〜４の整数である。ｎは０〜２の整数である。ｐは１〜６の整数である。）。

(In the formulas (II) to (VII), R ⁷ and R ⁸ each represent a hydrocarbon group having 1 to 10 carbon atoms which may have an ether bond, an ester bond or an epoxy bond. R ⁹ Represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, and a and b are respectively C is an integer of 1 to 4 that satisfies 4-ab, n is an integer of 0 to 2, and p is an integer of 1 to 6.)

  Examples of the silane compound represented by the formula (II) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxy. Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, trimethylethoxysilane, methoxyethyltriethoxysilane, acetoxyethyltriethoxysilane, diethoxyethyl Dimethoxysilane, tetraacetoxysilane, methyltriacetoxysilane, tetrakis (2-methoxyethoxy) silane, γ-glycidoxypropi Trimethoxysilane, .gamma.-glycidoxypropylmethyldiethoxysilane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

Examples of the silane compound represented by the formula (III) include tetrakis (acryloyloxyethoxy) silane, tetrakis (methacryloyloxyethoxy) silane, methyltris (acryloyloxyethoxy) silane, and methyltris (methacryloyloxyethoxy) silane. .
Examples of the silane compound represented by the formula (IV) include β-acryloyloxyethyldimethoxymethylsilane, γ-acryloyloxypropylmethoxydimethylsilane, γ-acryloyloxypropyltrimethoxysilane, and β-methacryloyloxyethyldimethoxymethyl. Examples include silane and γ-methacryloyloxypropyltrimethoxysilane.

  Examples of the silane compound represented by the formula (V) include vinylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

  Examples of the silane compound represented by the formula (VI) include γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane.

  Examples of the silane compound represented by the formula (VII) include p-vinylphenylmethyldimethoxysilane and p-vinylphenyltrimethoxysilane. These silane compounds may be used individually by 1 type, and may use 2 or more types together.

The method for adding the inorganic fine particles (B) is not particularly limited. For example, after the thermoplastic resin (A) having a functional group curable on the side chain by active energy rays is polymerized in advance, the inorganic fine particles (B) Or a mixture of the monomer constituting the thermoplastic resin (A) having a functional group curable with active energy rays in the side chain and the inorganic fine particles (B). Any method such as a method of polymerizing monomers can be selected.
Moreover, as content in the case of adding an inorganic fine particle (B) in the resin composition for obtaining resin (X), in 100 mass% of resin components of a resin composition, it exists in the range of 10-80 mass%. Preferably there is. By making it 10% by mass or more, it becomes possible to impart pencil hardness to the resin (X), and by making it 80% by mass or less, maintaining flexibility while imparting pencil hardness to the resin (X). Is possible. More preferably, it is 20-75 mass%, More preferably, it exists in the range of 30-70 mass%.

<Polyfunctional monomer (C)>
The resin composition for producing the resin (X) of the present invention may contain a polyfunctional monomer (C) as necessary. By containing the polyfunctional monomer (C), it is possible to impart flexibility and restorability to the resin (X) obtained by curing.

  Although there is no restriction | limiting in particular as a polyfunctional monomer (C), From a reactive viewpoint with the thermoplastic resin (A) which has a functional group which can be hardened by an active energy ray in the side chain mentioned above, polyfunctional ( A meth) acrylate is preferred.

  Examples of such polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butylene glycol dimethacrylate, and 1,6-hexanediol diene. Methacrylate, 2-methyl-1,3-propanediol dimethacrylate, neopentyl glycol di (meth) acrylate, 2,2'-dimethyl-1,4-butanediol dimethacrylate, trimethylolpropane tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dicyclopentadienyl dimethacrylate, polyethylene glycol di (meth) acrylate, poly Examples include propylene glycol di (meth) acrylate and polybutylene glycol (meth) acrylate. These may be used alone or in combination of two or more.

  Among them, a polyfunctional monomer having a repeating unit of a polyalkylene glycol chain represented by polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyhexamethylene glycol di (meth) acrylate, etc. However, it is preferable because flexibility and resilience can be imparted to the obtained resin. Moreover, it is more preferable that it is the polyfunctional monomer whose repeating unit of a polyalkylene glycol chain exists in the range of 3-40, and it is still more preferable that it exists in the range of 6-30. By setting the repeating unit within the range of 3 to 40, it is possible to maintain the hardness while imparting flexibility and restorability to the obtained resin.

Specific examples of commercially available polyfunctional monomers having a repeating unit of a polyalkylene glycol chain include, for example, Aronix M-240, Aronix M-260, Aronix M-270 (all trade names, Toa Gosei Co., Ltd.) Product), NK ester A-400, NK ester A-600, and NK ester A-1000 (all are trade names, manufactured by Shin-Nakamura Chemical Co., Ltd.).
The content of the polyfunctional monomer (C) in the resin composition for obtaining the resin (X) is preferably 50% by mass or less in 100% by mass of the resin component of the resin composition. By containing 50 mass% or less, it becomes possible to improve a softness | flexibility and a recoverability, without impairing the pencil hardness of resin (X). More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less.

<Polyfunctional thiol compound (D)>
In the resin composition for manufacturing resin (X) of this invention, a polyfunctional thiol compound (D) can be contained as needed. The polyfunctional thiol compound (D) is a compound having two or more thiol groups in one molecule. By containing the polyfunctional thiol compound (D), it becomes possible to impart further flexibility and resilience to the resin (X) obtained by curing.
Moreover, the thermoplastic resin (A) and the polyfunctional thiol compound (D) having a functional group that can be cured by active energy rays in the side chain can be cured by heating in the presence of a catalyst. In this case, if the thermoplastic resin (A) is a resin having an α, β unsaturated carbonyl group, a reaction utilizing Michael addition between the α, β unsaturated carbonyl group and the polyfunctional thiol compound (D) is effective. It is preferable because it is possible to proceed.
The resin (X) thermoset using the polyfunctional thiol compound (D) is excellent in flexibility and thus can be easily molded. Moreover, since the tackiness is reduced by curing, it is possible to suppress the transfer of the resin (X) to the mold and the transfer of the unevenness on the mold surface. After molding, it is possible to obtain a molded product having flexibility and restorability by further curing using an active energy ray.

There is no restriction | limiting in particular as a polyfunctional thiol compound (D), A well-known thing can be used. Specific examples of the polyfunctional thiol compound (D) include, for example, 1,2-ethanedithiol, 1,4-bis (3-mercaptobutyryloxy) butane, tetraethylene glycol bis (3-mercaptopropionate), Trimethylol ethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol Tetrakis (3-mercaptopropionate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, tris -[(3-Mercaptopropionyloxy) -ethyl] -isocyanate Rate, dipentaerythritol diethylcarbamoyl Sri tall hexakis (3-mercaptopropionate) and the like.
Among them, the polyfunctional thiol compound (D) having 2 to 10 thiol groups is preferable from the viewpoint of flexibility and moldability of the obtained resin (X). If there are two or more thiol groups, it is possible to impart flexibility and moldability while reducing the tackiness when the resin composition is heat-cured, and the resin ( It becomes possible to maintain the moldability after thermosetting without impairing the flexibility of X).
Specific examples of commercially available products of the polyfunctional thiol compound (D) include, for example, “Karenz MT PE1”, “Karenz MT NR1”, “Karenz MT PE1” (all trade names, manufactured by Showa Denko KK) TMMP "," TEMPIC "," PEMP "," DPMP "," EGMP-4 "(all are trade names, manufactured by SC Organic Chemical Co., Ltd.) and the like.
As addition amount of a polyfunctional thiol compound (D), it is preferable that it is 0.1-10 mass parts. By adding 0.1 to 10 parts by mass or more, it is possible to heat and thermally cure the resin composition while imparting flexibility and resilience, and it is preferable without impairing moldability. More preferably, it is 0.3-9 mass parts, More preferably, it is 0.5-8 mass parts.

  Moreover, there is no restriction | limiting in particular as a catalyst used for thermosetting, A well-known catalyst can be used. As the catalyst used in the Michael addition reaction, for example, a basic compound is preferably used. Examples of basic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide and potassium ethoxide; tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide. Quaternary ammonium carbonates such as tetrabutylammonium carbonate and benzyltrimethylammonium carbonate; quaternary ammonium fluorides such as tetrabutylammonium fluoride and benzyltrimethylammonium fluoride; tetrabutylammonium tetrahydroborate and benzyltrimethylammonium tetrahydro Quaternary ammonium tetrahydroborate such as borate; tetramethylgua Tertiary amines such as niidine, 1,8-diazabicyclo [5,4,0] undecene-7, diazabicyclo [4,3,0] nonene-5; tertiary phosphines such as guanidine, amidine and triphenylphosphine, etc. Is mentioned. As the basic compound of the catalyst, it is preferable to use a tertiary amine and / or a tertiary phosphine.

<Photopolymerization initiator (E)>
As the photopolymerization initiator (E) necessary for curing the resin composition containing the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain of the present invention, for example, an electron beam And photoradical polymerization initiators that generate radicals by irradiation with active energy rays such as ultraviolet rays or visible rays.
As the radical photopolymerization initiator, known compounds can be used and are not particularly limited. In consideration of yellowing during photocuring and deterioration during weathering, compounds such as acetophenone, benzophenone, and acylphosphine oxides that do not contain an amino group in the molecule are preferred. For example, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. These may be used alone or in combination of two or more.

  As the content of the photopolymerization initiator (E), since the residual amount after curing affects the weather resistance, the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain, indefinite fine particles ( 0.1-5 mass parts is preferable with respect to a total of 100 mass parts of B) and a polyfunctional monomer (C). Moreover, when using the amino-type radical photopolymerization initiator in connection with yellowing at the time of hardening as a photoinitiator (E), 1 mass part or less is preferable.

  The method for adding the photopolymerization initiator (E) to the resin composition is not particularly limited. For example, after polymerizing a thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain in advance, a photopolymerization initiator (E) may be mixed, or a radically polymerizable unsaturated group in the side chain. Arbitrary methods, such as a method of polymerizing the monomer, can be selected under the condition where the monomer constituting the thermoplastic resin (A) having a photopolymerization initiator (E) is mixed.

<Method of curing resin composition>
The method for curing the resin composition for obtaining the resin (X) of the present invention is not particularly limited, and a known curing method such as irradiation with active energy rays such as heat, electron beam, ultraviolet ray or visible ray is appropriately selected. Can be used. Moreover, these methods can be used in combination for curing. Examples of the active energy ray may further include heat rays such as plasma and infrared rays. Among the active energy rays, it is preferable to use ultraviolet rays that are widely used from the viewpoint of introduction of facilities and management of illuminance.
As the curing method, as described above, from the viewpoint of the reaction rate when obtaining the resin (X) and the necessity of considering the heat resistance of the base material when curing, a curing method by irradiation with ultraviolet rays is used. It is preferable to use it.
As for the timing of curing, it is preferable to apply a resin composition for obtaining the resin (X) on a substrate by a coating method described later, dry the solvent, and then cure by irradiating with ultraviolet rays.
Irradiation conditions can be arbitrarily set, but are usually about 100 to 10,000 mJ / cm ^{2 in} terms of irradiation energy.

Moreover, when the polyfunctional thiol compound (D) mentioned above is used, it can also be hardened | cured with a heat | fever. In the case of curing by heat, the drying temperature is preferably in the range of 60 to 100 ° C. from the viewpoint of tackiness of the obtained resin (X). By setting the temperature within the range of 60 to 100 ° C., the reaction between the thermoplastic resin (A) having a functional group curable with active energy rays in the side chain and the polyfunctional thiol compound (D) can be efficiently advanced. It becomes. The heating time is not particularly limited as long as it is longer than the tackiness of the obtained resin (X), and can be appropriately determined by confirming the properties of the resin (X).
Here, from the viewpoint of imparting flexibility and resilience to the resin (X), it is preferable that the resin (X) is further cured using an active energy ray after thermosetting. As the active energy ray, the same kind of the above-mentioned kind can be used under the same conditions.

<Base material>
Examples of the base material used when laminating the resin (X) of the present invention include ABS (acrylonitrile / butadiene / styrene copolymer) resin, AS (acrylonitrile / styrene copolymer) resin, and vinyl chloride resin. Resin, polystyrene resin, polyolefin resin such as polypropylene, fluorine resin, cellophane resin, cellulose resin, polyurethane resin, polyamide resin such as nylon, polyester resin, polycarbonate resin, polyvinyl alcohol resin, ethylene Examples thereof include a sheet using at least one resin selected from thermoplastic resins such as vinyl alcohol resins and acrylic resins. Moreover, these base materials can also be used by stacking two or more sheets.

  In view of adhesion between the resin (X) and the substrate, weather resistance, transparency and the like, it is preferable to use a sheet made of an acrylic resin. Further, a thermoplastic acrylic resin sheet having a crosslinked rubber component is more preferable from the viewpoint of handling.

In the base material, various additives such as lubricants such as polyethylene wax and paraffin wax, lubricants such as silica, spherical alumina and scaly alumina, plasticizers, stabilizers and colorants are blended as necessary. be able to.
For example, when using the laminated body by which resin (X) was laminated | stacked on the base material outdoors, it is preferable to mix | blend a ultraviolet absorber and a light stabilizer in a base material. Examples of the ultraviolet absorber and the light stabilizer include the same as those described in the section of the resin (X).
The thickness of the substrate is preferably within a range of 0.01 to 5 mm. The range of 0.02 to 4 mm is more preferable, and the range of 0.03 to 3 mm is more preferable. The thickness of the substrate can be appropriately selected and used depending on the application. It is preferable to use a film-shaped base material from the viewpoint of cost and handleability of the laminate described later.

<Laminate>
As a laminated body concerning the aspect of this invention, what laminated | stacked the layer of resin (X) on the at least one surface of a base material is mentioned. Moreover, the decoration layer and / or adhesive layer which are mentioned later can be laminated | stacked on the surface opposite to the layer of resin (X) provided in the base material of the laminated body as needed.
As a method of laminating the resin (X) layer on the substrate, for example, after applying a solution of the resin composition for obtaining the resin (X) on the substrate sheet, the organic solvent is dried. And a method of obtaining a laminated sheet.
In addition, when the resin material used for the base material is a polyolefin resin such as polyethylene or polypropylene having low adhesiveness to the resin (X), the adhesiveness between the base material and the resin (X) is improved. In order to achieve this, it is preferable to apply a primer composed of a low molecular weight polyolefin or the like in advance on the substrate, or to activate the surface of the substrate in advance by corona discharge or the like.

In addition, when performing said corona discharge, it is preferable to carry out just before laminating | stacking resin (X) from a viewpoint of the adhesiveness of resin (X) and a base material.
Furthermore, when the resin (X) is cured with active energy rays, a primer layer is provided between the substrate and the resin (X) for the purpose of preventing volume shrinkage and lowering the adhesion to the substrate. Can be formed.

  Examples of the method for laminating the resin (X) include known coating methods such as a knife coating method, a comma coating method, a reverse coating method, and a dip coating method, or a method similar to a printing layer forming method described later.

<Molded body>
When the resin composition containing the polyfunctional thiol compound (D) described above is used, after making a laminate having a layer of the resin composition, the laminate is thermally cured and molded into a desired shape. Further, by curing the layer of the resin composition after thermosetting with active energy rays, it is possible to obtain a molded body imparted with flexibility and restorability.
By thermally curing the resin composition layer once, it becomes possible to reduce the tackiness, so that the resin can be easily molded.
As the conditions for thermosetting the resin composition, the conditions described in the section of the method for curing the resin composition can be used.
In addition, as the active energy ray, the same kind of the above-mentioned kind can be used under the same conditions.

There is no restriction | limiting in particular as a shaping | molding method, A well-known shaping | molding method can be used. Examples of the molding method include an insert molding method, an in-mold molding method, and a three-dimensional overlay laminate molding method.
The insert molding method means that a film or sheet that has been decorated such as printing is formed in advance into a three-dimensional shape by vacuum forming or the like, and unnecessary film or sheet portions are removed by trimming, and then an injection mold. This is a method for obtaining a molded body by integrating the resin by injection molding the resin to be a base material.
The in-mold molding method is to place a film or sheet that has been decorated such as printing in an injection mold, perform vacuum molding, and then injection mold a resin as a base material in the same mold This is a method for obtaining a molded body by integrating them.

The three-dimensional overlay laminate molding method refers to the following method.
First, two sealed spaces partitioned by a sheet are formed, a molded body is disposed on one side of the space, and only the space where both the spaces or the molded body is disposed is decompressed.
Next, the sheet is softened by heating, and in a state where the molded body is pressed against the sheet surface from one space side to the other space side, only the other space where the molded body is not disposed is returned to normal pressure, The sheet is attached to the molded body using pressure.
In the three-dimensional overlay laminate molding method, the heated sheet is uniformly applied with pressure to the surface of the molded body, so that even if the surface of the molded body is curved, the sheet is satisfactorily adhered to the molded body. Can be attached.
As an apparatus for performing the three-dimensional overlay laminate molding, for example, “TOM (trade name)” manufactured by Fuse Vacuum Co., Ltd. may be mentioned.

  When manufacturing this molded object by injection molding, as a resin material used for a base material, the resin material in which the shrinkage rate after injection molding approximated the shrinkage rate of a film or a sheet is preferable. When the shrinkage ratios of both companies are close to each other, there is a tendency that problems such as warpage of a molded body obtained by in-mold molding or insert molding, or peeling of a film or a sheet do not easily occur.

<Protective sheet>
In the laminate according to the aspect of the present invention, a protective sheet can be laminated on the resin (X) layer of the laminate as necessary. The protective sheet is effective for preventing dust on the surface of the resin (X) layer, and is also effective for preventing the resin (X) layer from being damaged by movement due to conveyance or the like.
The protective sheet is in close contact with the resin (X) layer, and is processed while being peeled or bonded before use of the laminate, and then peeled off. Therefore, the protective sheet has appropriate adhesion to the resin (X) layer. It is preferable to have good releasability.
Any protective sheet that satisfies such conditions can be selected and used. Examples of such a protective sheet include a polyethylene film, a polypropylene film, and a polyester film.

<Decoration layer>
The laminated body concerning the aspect of this invention can be laminated | stacked with the decoration layer comprised by at least 1 sort (s) chosen from the printing layer and vapor deposition layer which are mentioned later as needed.
The decoration layer concerning the aspect of this invention is laminated | stacked in order to give decorations, such as a pattern and a character, to the surface of a laminated body. Any kind of decoration can be selected, and examples thereof include wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, and solid pattern.

<Print layer>
As a material used for a printing layer, the coloring ink containing a resin binder and a coloring agent is mentioned, for example.
Examples of the resin binder include polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, and cellulose. Examples include ester resins, alkyd resins, and chlorinated polyolefin resins.

Examples of the colorant include at least one selected from known dyes and pigments. Examples of pigments include, for example, azo pigments such as polyazo, organic pigments such as isoindolinone, yellow pigments such as inorganic pigments such as yellow lead; azo pigments such as polyazo, organic pigments such as quinacridone, and inorganics such as petals Red pigments such as pigments; organic pigments such as phthalocyanine blue; blue pigments such as inorganic pigments such as cobalt blue; black pigments such as aniline black; and white pigments such as titanium dioxide.
Examples of the method for forming the printing layer include a printing method such as an offset printing method, a gravure rotary printing method and a screen printing method, and a coating method such as a roll coating method and a spray coating method.

<Deposition layer>
Examples of the material used for the vapor deposition layer include at least one metal selected from aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead and zinc, or an alloy or metal thereof. Compounds.
Examples of the method for forming the vapor deposition layer include a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method.

<Adhesive layer>
The adhesive layer concerning the aspect of this invention can be formed as needed, when the adhesiveness improvement of a laminated body and a decoration layer is desired, or when a sheet-like base material is further laminated | stacked on a laminated body.
There is no restriction | limiting in particular as a material used for a contact bonding layer, Arbitrary synthetic resin materials etc. can be selected suitably, and can be used.
Materials used for the adhesive layer include, for example, polyacrylic resins, polyphenylene oxide / polystyrene resins, polycarbonate resins, styrene copolymer resins, polyamide resins, chlorinated polyolefin resins, and chlorinated ethylene-vinyl acetate copolymers. Examples include system resins, cyclized rubbers, coumarone indene resins, and thermosetting urethane resins using blocked isocyanates. Resins used for these adhesive layers may be used alone or in combination of two or more depending on the purpose.

In addition, hydrophobic silica, an epoxy resin, a petroleum resin, etc. can be mix | blended with a contact bonding layer as needed for the purpose of the adhesiveness reduction of a contact bonding layer, or heat resistance improvement.
Examples of the method for forming the adhesive layer include the same methods as those described in the section of the laminate and the printed layer.

  Applications of the resin and laminate of the present invention include, for example, automotive interior components such as instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, and dashboards; weather strips, bumpers , Bumper guards, side mud guards, body panels, spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, head lamp covers, tail lamp covers, windshield parts, etc. Automotive exterior members; various front panels for AV equipment; surface cosmetics such as buttons and emblems; various parts such as mobile phone housings, display windows and buttons; Exterior materials for buildings; Interior materials for buildings such as walls, ceilings, floors; Exterior walls for walls such as siding, fences, roofs, gates, and windbreak boards; Furniture such as window frames, doors, handrails, sills, and duck Surface cosmetic materials; Optical members such as various displays, lenses, mirrors, goggles and window glass; Members for interior and exterior of various vehicles other than automobiles such as trains, airplanes and ships; and various packaging such as bottles, cosmetic containers, and accessory cases Various other uses such as miscellaneous goods such as containers, packaging materials, prizes, and accessories can be mentioned.

  In the following, embodiments of the present invention will be specifically described based on examples, but it goes without saying that the scope of the present invention is not limited thereto. In the examples, “parts” means “parts by mass”. In addition, various measurements and evaluations in this example were performed by the following methods.

(1) Solid content Solid content was measured with the following method.
About 0.5 g of a solution or dispersion of a thermoplastic resin (A) or resin composition (X ′) having a functional group curable by active energy rays in the side chain is collected on an aluminum dish and an accurate mass is measured. did. After volatilizing the solvent or dispersion medium at room temperature, the mass of the solid obtained by heating at 80 ° C. for 4 hours was measured, and the solid content (% by mass) was calculated.

(2) Mass average molecular weight (Mw)
Mw of the thermoplastic resin (A) having a functional group curable with active energy rays in the side chain was measured using a high-speed GPC apparatus (manufactured by Tosoh Corporation, model: HLC-8220 GPC). In addition, about the numerical value, the value converted into polystyrene was used.

(3) Double bond equivalent The double bond equivalent of the thermoplastic resin (A) having a radically polymerizable unsaturated group in the side chain is estimated by estimating the structure of the acrylic resin (A) from the synthetic formula, (G / mol) was calculated.

(4) Glass transition temperature (Tg)
The Tg of the thermoplastic resin (A) having a functional group curable by active energy rays in the side chain was calculated from the synthesis prescription using the formula of FOX.
For the 4-hydroxybutyl acrylate glycidyl ether used in the synthesis, the value described in the catalog of Nippon Kasei Co., Ltd. (homopolymer Tg: −64 ° C.), and for the (meth) acrylic macromonomer, refer to the polymer handbook [ Polymer Handbook (J. Brandrup, Interscience, 1989)], the value of methyl methacrylate (homopolymer Tg: 105 ° C.), and the silicone-based macromonomer, the polydimethylsiloxane described in the Polymer Handbook The value (Tg: −123 ° C.) was used.

ここで、復元率（ｘ）は上記測定条件で測定され、算出に用いたＬｓ，Ｌｅ，Ｌｍａｘはそれぞれ、Ｌｓ：荷重を加え始めた際の初期の押込み深さ、Ｌｅ：除荷後、更に２５秒間保持した後の押込み深さ、Ｌｍａｘ：５ｍＮで１０秒保持した後の最も深く圧子が押し込まれた際の押込み深さ、である。 (5) Restoration rate It measured on the following measurement conditions, and the restoration rate was computed by following formula (1).
Measurement conditions Equipment: Micro hardness tester Fischer scope HM2000
(Fischer Instruments)
Indenter: Vickers indenter (four-sided diamond cone)
Test atmosphere: temperature 23 ° C, humidity 50%
Measurement program:
On the surface of the resin (X) layer, the load was applied to the Vickers indenter while gradually increasing the load under the condition of 5 mN / 5 seconds. After reaching 5 mN, the load was held for 10 seconds. The load is unloaded while decreasing the load with, and after unloading, hold for 25 seconds.

Here, the restoration rate (x) is measured under the above measurement conditions, and Ls, Le, and Lmax used for the calculation are Ls: initial indentation depth when the load is started, Le: after unloading, and further, The indentation depth after being held for 25 seconds, Lmax: the indentation depth when the indenter was most deeply pushed in after being held at 5 mN for 10 seconds.

(6) Indentation elastic modulus The indentation elastic modulus (MPa) calculated based on the standard of ISO14577 was used as it was when measured by the same method as the method of measuring the restoration rate.

(7) Martens hardness The Martens hardness (N / mm ² ) calculated based on the ISO 14577 standard was used as it was when measured by the same method as the method for measuring the restoration rate.

(8) Total light transmittance and haze Total light transmittance and haze were measured using a haze meter (Nippon Denshoku Industries Co., Ltd., model: NDH4000).

(9) Pencil hardness In accordance with JIS K5600-5-4, a pencil (Mitsubishi Pencil Co., Ltd., product name: uni) was used for evaluation.
(10) Scratch resilience Using a ballpoint pen with a tip having a width of about 1.0 mm, the surface of the obtained resin is scratched with enough strength to be pushed in with the ballpoint pen, and the presence or absence of restoration of the scratch is visually determined. did.
○: After scratching, the scratch is restored and the original state is restored.
X: After scratching, scratches are not restored and can be visually confirmed as scratches.

[Synthesis Example 1] Synthesis of a thermoplastic resin (A-1) having a functional group curable by active energy rays in the side chain In a 300 mL four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, 75 parts of methyl ethyl ketone was added as a solvent, and the temperature was raised to 80 ° C.
The flask was then placed under a nitrogen atmosphere, and monomer components of 30 parts of methyl ethyl ketone, 78.4 parts of butyl acrylate, 21.6 parts of 4-hydroxybutyl acrylate glycidyl ether and 0.35 parts of azobisisobutyronitrile (a) ) Was added dropwise over 2 hours, followed by stirring for 1 hour.
Thereafter, a mixture of 30 parts of methyl ethyl ketone and 0.15 part of azobisisobutyronitrile was added dropwise over 30 minutes with stirring.
After stirring for another 5 hours and 30 minutes, 67.4 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine, and 7.7 parts of acrylic acid 7.7 parts are added for 30 minutes. The mixture was added dropwise and stirred at 80 ° C. for 40 hours while blowing air.
Next, after cooling the inside of the flask and adding methyl ethyl ketone in a volatilized amount, the reaction product is taken out from the flask, and a solution of the thermoplastic resin (A-1) having a functional group that can be cured by active energy rays in the side chain. Obtained.

The solid content of the thermoplastic resin (A-1) is about 35% by mass, the Mw is about 52,000, the calculated double bond equivalent is about 999 g / mol, and the formulation of only the monomer component (A) The Tg calculated from the formula of FOX of the polymer obtained from the above was about -56 ° C.
The synthesis is summarized in Table 1.

[Synthesis Example 2] Synthesis of a thermoplastic resin (A-2) having a functional group curable by active energy rays in the side chain In a 300 mL four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, 105 parts of methyl ethyl ketone as a solvent, 12 parts of ELVACITE 1020 (manufactured by Lucite, Mw: 11,000) as a (meth) acrylic macromonomer, and X-22-174DX (Shin-Etsu Chemical Co., Ltd.) as a silicone-based macromonomer Manufactured, one-end methacryl-modified silicone oil, Mw: 66,000), and stirred while heating to 80 ° C. to dissolve the macromonomer in methyl ethyl ketone.
The flask was then placed under a nitrogen atmosphere, and monomer components (ii) of 30 parts methyl ethyl ketone, 47 parts butyl acrylate, 35 parts 4-hydroxybutyl acrylate glycidyl ether and 0.35 parts azobisisobutyronitrile were added for 2 hours. The mixture was added dropwise and stirred for 1 hour after the addition.
Thereafter, a mixture of 12.5 parts of methyl ethyl ketone and 0.15 part of azobisisobutyronitrile was added dropwise with stirring over 30 minutes.
After further stirring for 5 hours and 30 minutes, 58 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine and 12.5 parts of acrylic acid were added over 30 minutes. The solution was added dropwise and stirred at 80 ° C. for 40 hours while blowing air.
Next, after cooling the inside of the flask and adding methyl ethyl ketone in a volatilized amount, the reaction product is taken out of the flask, and a solution of the thermoplastic resin (A-2) having a functional group curable by active energy rays in the side chain is added. Obtained.

The solid content of the thermoplastic resin (A-2) is about 35% by mass, the Mn is about 37,000, the calculated double bond equivalent is about 644 g / mol, and the formulation of only the monomer component (a) The Tg calculated from the formula of FOX of the polymer obtained from the above was about -47 ° C.
The synthesis is summarized in Table 1.

[Synthesis Example 3] Synthesis of a thermoplastic resin (A-3) having a functional group curable by active energy rays in the side chain In a 300 mL four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, Add 105 parts of methyl ethyl ketone as a solvent and 13.2 parts of ELVACITE 1020 (manufactured by Lucite, Mw: 11,000) as a (meth) acrylic macromonomer, stir while raising the temperature to 80 ° C., and add the macromonomer to methyl ethyl ketone. Dissolved.
The flask was then placed under a nitrogen atmosphere, and monomer components of 30 parts methyl ethyl ketone, 32.9 parts butyl acrylate, 52.9 parts 4-hydroxybutyl acrylate glycidyl ether and 0.35 parts azobisisobutyronitrile (I ) Was added dropwise over 2 hours, followed by stirring for 1 hour.
Thereafter, a mixture of 12.5 parts of methyl ethyl ketone and 0.15 part of azobisisobutyronitrile was added dropwise with stirring over 30 minutes.
After further stirring for 5 hours 30 minutes, 54 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine, and 18.9 parts of acrylic acid were added over a period of 30 minutes. The solution was added dropwise and stirred at 80 ° C. for 40 hours while blowing air.
Next, after cooling the inside of the flask and adding methyl ethyl ketone in a volatilized amount, the reaction product is taken out from the flask, and a solution of the thermoplastic resin (A-3) having a functional group that can be cured by active energy rays in the side chain. Obtained.

The solid content of the thermoplastic resin (A-3) is about 36% by mass, the Mn is about 40,000, the calculated double bond equivalent is about 450 g / mol, and the formulation containing only the monomer component (A) The Tg calculated from the formula of FOX of the polymer obtained from the above was about -47 ° C.
The synthesis is summarized in Table 1.

[Synthesis Example 4] Synthesis of a thermoplastic resin (A-4) having a functional group curable by active energy rays in the side chain In a 300 mL four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, 75 parts of methyl ethyl ketone was added as a solvent, and the temperature was raised to 80 ° C.
The flask was then placed under a nitrogen atmosphere, and monomer components (a) of 30 parts of methyl ethyl ketone, 94.2 parts of butyl acrylate, 7.6 parts of 4-hydroxybutyl acrylate glycidyl ether and 0.35 parts of azobisisobutyronitrile. ) Was added dropwise over 2 hours, followed by stirring for 1 hour.
Thereafter, a mixture of 30 parts of methyl ethyl ketone and 0.15 part of azobisisobutyronitrile was added dropwise over 30 minutes with stirring.
After further stirring for 5 hours and 30 minutes, 34 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine and 2.7 parts of acrylic acid were added over 30 minutes. The solution was added dropwise and stirred at 80 ° C. for 40 hours while blowing air.
Next, after cooling the inside of the flask and adding methyl ethyl ketone in a volatilized amount, the reaction product is taken out from the flask, and a solution of the thermoplastic resin (A-4) having a functional group that can be cured by active energy rays in the side chain. Obtained.
The solid content of the thermoplastic resin (A-4) is about 38% by mass, the Mw is about 72,000, the calculated double bond equivalent is about 3797 g / mol, and the formulation containing only the monomer component (A) The Tg calculated from the formula of FOX of the polymer obtained from the above was about −55 ° C.
The synthesis is summarized in Table 1.

[Synthesis Example 5] Synthesis of a thermoplastic resin (A-5) having a functional group curable by active energy rays in the side chain In a 300 mL four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, 75 parts of methyl ethyl ketone was added as a solvent, and the temperature was raised to 80 ° C.
The flask was then placed under a nitrogen atmosphere, and monomer components of 30 parts of methyl ethyl ketone, 85.2 parts of butyl acrylate, 14.8 parts of 4-hydroxybutyl acrylate glycidyl ether and 0.35 parts of azobisisobutyronitrile (I ) Was added dropwise over 2 hours, followed by stirring for 1 hour.
Thereafter, a mixture of 30 parts of methyl ethyl ketone and 0.15 part of azobisisobutyronitrile was added dropwise over 30 minutes with stirring.
After further stirring for 5 hours and 30 minutes, 39 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine and 5.3 parts of acrylic acid were added over 30 minutes. The solution was added dropwise and stirred at 80 ° C. for 40 hours while blowing air.
Next, after cooling the inside of the flask and adding methyl ethyl ketone in a volatilized amount, the reaction product is taken out from the flask, and a solution of the thermoplastic resin (A-5) having a functional group curable with active energy rays in the side chain is added. Obtained.
The solid content of the thermoplastic resin (A-5) is about 38% by mass, the Mw is about 72,000, the calculated double bond equivalent is about 1426 g / mol, and the formulation of only the monomer component (A) The Tg calculated from the formula of FOX of the polymer obtained from the above was about −55 ° C.
The synthesis is summarized in Table 1.

[Synthesis Example 6] Synthesis of a thermoplastic resin (A-6) having a functional group curable by active energy rays in the side chain In a 300 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, 70 parts of methyl ethyl ketone was added as a solvent, and the temperature was raised to 80 ° C.
Next, the inside of the flask was placed in a nitrogen atmosphere, and the monomer component (I) of 30 parts of methyl ethyl ketone, 80 parts of methyl methacrylate, 20 parts of glycidyl methacrylate and 0.5 part of azobisisobutyronitrile was added dropwise over 4 hours. Stirring was performed for 1 hour after the dropping.
Thereafter, a mixture of 30 parts of methyl ethyl ketone and 0.2 part of azobisisobutyronitrile was added dropwise over 30 minutes with stirring.
The mixture was further stirred for 5 hours and 30 minutes, and then 67.4 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine and 10.1 parts of acrylic acid were added for 30 minutes. The mixture was added dropwise and stirred at 80 ° C. for 35 hours while blowing air.
Next, after the flask was cooled, methyl ethyl ketone was added after volatilization, and the reaction product was taken out of the flask and a solution of a thermoplastic resin (A-6) having a functional group curable with active energy rays in the side chain. Got.

The solid content of the thermoplastic resin (A-6) is about 36% by mass, the Mw is about 52,000, the calculated double bond equivalent is about 781 g / mol, and the formulation of only the monomer component (A) The Tg calculated from the formula of FOX of the polymer obtained from was about 91 ° C.
The synthesis is summarized in Table 1.

[Synthesis Example 7] Synthesis of inorganic fine particles (B) In a 3 L four-necked flask equipped with a stirrer, a thermometer and a condenser, methanol silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MT-ST, dispersion medium: 1200 parts of methanol, SiO ₂ concentration: 30% by mass, primary particle size: 10-20 nm) and γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KBM-503, molecular weight) as an organic silane compound : 248) 230 parts were added and heated with stirring.
After reflux of the volatile components started, 33 parts of pure water was added and hydrolysis was performed with stirring for 2 hours under reflux to distill off volatile components such as alcohol and water, so that the solid content concentration reached 60% by mass. It adjusted so that it might become.
Thereafter, 700 parts of toluene was added, and alcohol, water and the like were azeotropically distilled together with toluene for 3 hours while stirring. Furthermore, in order to perform solvent substitution completely, it reacted at 110 degreeC for 4 hours, distilling alcohol and toluene, and solid content concentration was set to about 60 mass%.

[Example 1]
1-Hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, molecular weight: 204.3, manufactured by BASF) as the thermoplastic resin (A-1), inorganic fine particles (B) and photopolymerization initiator (E) Was used as a solution of the resin composition (X′-1). Furthermore, methyl ethyl ketone was added to adjust the solid content so that the solid content in the resin composition (X′-1) was 35% by mass.
On one side of the acrylic resin (Mitsubishi Rayon Co., Ltd., trade name “Acrylite L”, thickness 3 mm, transparent) cut into A4 size using the obtained resin composition (X′-1) as a base material After coating with a coating width of 180 mm, it was dried for 3 minutes using a hot air dryer at 80 ° C. to obtain a laminated sheet in which a layer of resin (X-1) having a thickness of about 18 μm was laminated on the substrate.
The obtained laminated sheet was irradiated with ultraviolet rays of about 560 mJ / cm ² using an ultraviolet irradiation device (trade name: Igrantage (trademark) (4 kw) ECS-401GX, manufactured by Eye Graphics Co., Ltd.). The resin layer was cured to obtain a laminated sheet in which layers made of the cured resin were laminated.

The obtained laminated sheet had a total light transmittance of 93% and a haze of 0.5%, and exhibited excellent transparency.
Further, since the thermoplastic resin (A-1) having a side chain and the inorganic fine particles (B) are used in combination with a low Tg polymer, the obtained resin has a recovery rate of 86.5% and an indentation elastic modulus. Of 1280 MPa, Martens hardness of 77 N / mm ² , and pencil hardness of H, which were confirmed to exhibit flexibility, restorability and hardness.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 2]
Instead of the thermoplastic resin (A-1), a thermoplastic resin (A-2) was used, and a layer of the resin (X-2) was obtained as a resin composition (X′-2) in the ratio shown in Table 2. Except for this, the same procedure as in Example 1 was performed.
The obtained laminated sheet had a total light transmittance of 93% and a haze of 0.5%, and exhibited excellent transparency.
Since the thermoplastic resin (A-2) having a low Tg and a side chain and inorganic fine particles (B) were used in the same manner as in Example 1, the obtained resin had a restoration rate of 76.4%. The indentation elastic modulus was 1600 MPa, the Martens hardness was 87 N / mm ² , and the pencil hardness was 2H, and it was confirmed that flexibility, restorability and high hardness were exhibited.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 3]
Instead of the thermoplastic resin (A-1), the thermoplastic resin (A-3) is used, and “Aronix M-260” (polyethylene glycol diacrylate: repeated ethylene glycol chain) as the polyfunctional monomer (C). Unit = 14, manufactured by Toa Gosei Co., Ltd.), “BYK-UV3500” (polyether-modified polydimethylsiloxane having an acrylic group, manufactured by Big Chemie Japan Co., Ltd.) as a lubricant, and a resin composition having the composition shown in Table 2 The same procedure as in Example 1 was performed except that a layer of resin (X-3) was obtained as the product (X′-3).
The obtained laminated sheet had a total light transmittance of 92% and a haze of 0.3%, and exhibited excellent transparency.
As in Example 1, a polyfunctional monomer having a low Tg polymer, a side chain-containing thermoplastic resin (A-3) and inorganic fine particles (B), and a repeating structure of ethylene glycol chains Thus, the obtained resin has a recovery rate of 93.0%, an indentation elastic modulus of 550 MPa, a Martens hardness of 37 N / mm ² , and a pencil hardness of 4H, so extremely excellent flexibility, It was confirmed that resilience and extremely high hardness were exhibited.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 4]
Instead of “Aronix M-260” as the polyfunctional monomer (C), “NK ester A-1000” (polyethylene glycol diacrylate: repeating unit of ethylene glycol chain = 23, manufactured by Shin-Nakamura Chemical Co., Ltd.) Was performed in the same manner as in Example 3 except that a resin (X-4) layer was obtained as a resin composition (X′-4) having the composition shown in Table 2.
The obtained laminated sheet had a total light transmittance of 93% and a haze of 0.3%, and exhibited excellent transparency.
As in Example 1, a polyfunctional monomer having a low Tg polymer and a side chain-containing thermoplastic resin (A-3) and inorganic fine particles (B) and having a repeating structure of a longer ethylene glycol chain Since the resin was used in combination, the resulting resin had a recovery rate of 97.4%, an indentation elastic modulus of 530 MPa, a Martens hardness of 36 N / mm ² , and a pencil hardness of 2H. It was confirmed that the restoration property and the high hardness were exhibited.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 5]
Instead of using a lubricant, instead of the thermoplastic resin (A-3), a thermoplastic resin (A-6) was used, and a resin (X-5) was obtained as a resin composition (X′-5) having the composition shown in Table 2. ) Was carried out in the same manner as in Example 3 except that the above layer was obtained.
The obtained laminated sheet had a total light transmittance of 93% and a haze of 0.5%, and exhibited excellent transparency.
Although the thermoplastic resin (A-6) having a side chain obtained from a polymer exhibiting high Tg and the inorganic fine particles (B) are used in combination, a polyfunctional monomer having a repeating structure of an ethylene glycol chain is used. The combined use of the resulting resin shows a recovery rate of 75.4%, an indentation elastic modulus of 1490 MPa, a Martens hardness of 70 N / mm ² , and a pencil hardness of 2H. Expression was confirmed.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 6]
Instead of “Aronix M-260” as the polyfunctional monomer (C), “NK ester A-1000” (polyethylene glycol diacrylate: repeating unit of ethylene glycol chain = 23, manufactured by Shin-Nakamura Chemical Co., Ltd.) Was performed in the same manner as in Example 5 except that a resin (X-6) layer was obtained as a resin composition (X′-6) having the composition shown in Table 2.
A polyfunctional monomer having a repeating structure of a longer ethylene glycol chain, although the thermoplastic resin (A-6) having a side chain obtained from a polymer exhibiting a high Tg and the inorganic fine particles (B) are used in combination. Since the resin was used in combination, the obtained resin had a restoration rate of 81.2%, an indentation elastic modulus of 1390 MPa, a Martens hardness of 70 N / mm ² , and a pencil hardness of H. It was confirmed that hardness was developed.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 7]
In addition to the resin composition of Example 1, as the polyfunctional thiol compound (D), “Karenz MT BD1” (1,4-bis (3-mercaptobutyryloxy) butane, thiol group = 2, Showa Denko ( 4 parts) and 0.5 part of “BYK-UV3500” (polyether-modified polydimethylsiloxane having an acrylic group, manufactured by Big Chemie Japan Co., Ltd.) as a lubricant is added, and the resin composition (X′- 7) was obtained.
On one side of an acrylic plate (Mitsubishi Rayon Co., Ltd., trade name “Acrylite L”, thickness 3 mm, transparent) cut into A4 size using the obtained resin composition (X′-7) as a base material After coating with a coating width of 180 mm, it was dried for 15 minutes using a hot air dryer at 80 ° C. to obtain a laminated sheet in which a layer of resin (X-7) having a thickness of about 18 μm was laminated on the substrate. Further, the resin (X-7) obtained here was cured by heat, had no tackiness, and did not leave a fingerprint mark.
The laminated sheet was further irradiated with ultraviolet rays of about 560 mJ / cm ² using an ultraviolet irradiation device (trade name: Igrantage (trademark) (4 kw) ECS-401GX, manufactured by Eye Graphics Co., Ltd.), and a resin layer. Was cured to obtain a laminated sheet in which layers of cured resin were laminated.
The laminated sheet obtained after the ultraviolet irradiation had a total light transmittance of 93% and a haze of 0.4%, and exhibited excellent transparency.
Further, since the thermoplastic resin (A-1), the inorganic fine particles (B) and the polyfunctional thiol compound (D) which are low Tg polymers and have side chains are used, the obtained resin has a restoration rate of 86. .3%, indentation elastic modulus of 1310 MPa, Martens hardness of 76 N / mm ² , and pencil hardness of 2H were confirmed to exhibit flexibility, restorability and hardness.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 8]
Polyfunctional thiol compound (D) “Karenz MT BD1” in the resin composition of Example 7 (1,4-bis (3-mercaptobutyryloxy) butane, thiol group = 2, manufactured by Showa Denko KK) Was added in an amount of 6 parts to obtain a resin composition (X′-8).
The laminated sheet heat-cured by the same method as in Example 7 did not feel tacky and did not leave a fingerprint mark.
Furthermore, the laminated sheet obtained by curing under the same ultraviolet irradiation conditions as in Example 7 had a total light transmittance of 93% and a haze of 0.5%, and exhibited excellent transparency.
Moreover, since the thermoplastic resin (A-1), the inorganic fine particles (B), and the polyfunctional thiol compound (D) having a low Tg polymer and having side chains were used, the obtained resin had a restoration rate of 84. .6%, indentation elastic modulus of 1020 MPa, Martens hardness of 58 N / mm ² , and pencil hardness of 2H were confirmed to exhibit flexibility, restorability and hardness.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 9]
The polyfunctional thiol compound (D) in the resin composition of Example 7 was changed to “Karenz MT PE1” (pentaerythritol tetrakis (3-mercaptobutyrate), four thiol groups, manufactured by Showa Denko KK). The resin composition (X′-9) was obtained with an addition amount of 3.6 parts.
The laminated sheet heat-cured by the same method as in Example 7 did not feel tacky and did not leave a fingerprint mark.
Furthermore, the laminated sheet obtained by curing under the same ultraviolet irradiation conditions as in Example 7 had a total light transmittance of 93% and a haze of 0.5%, and exhibited excellent transparency.
Moreover, since the thermoplastic resin (A-1), the inorganic fine particles (B), and the polyfunctional thiol compound (D) having a low Tg polymer and having side chains were used, the obtained resin had a restoration rate of 84. .6%, indentation elastic modulus was 1020 MPa, Martens hardness was 58 N / mm ² , and pencil hardness was 3H, confirming that flexibility, resilience and hardness were exhibited.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 10]
In addition to the resin composition of Example 2, as the polyfunctional thiol compound (D), “Karenz MT BD1” (1,4-bis (3-mercaptobutyryloxy) butane, thiol group = 2, Showa Denko ( Co., Ltd.) and 0.5 parts of “BYK-UV3500” (polyether-modified polydimethylsiloxane having an acrylic group, manufactured by Big Chemie Japan Co., Ltd.) as a lubricant. '-10) was obtained.
The laminated sheet heat-cured by the same method as in Example 7 did not feel tacky and did not leave a fingerprint mark.
Furthermore, the laminated sheet obtained by curing under the same ultraviolet irradiation conditions as in Example 7 showed excellent transparency with a total light transmittance of 93% and a haze of 0.4%.
Further, since the thermoplastic resin (A-2), the inorganic fine particles (B), and the polyfunctional thiol compound (D) having a low Tg polymer and having side chains were used, the obtained resin had a restoration rate of 83. .6%, indentation elastic modulus of 630 MPa, Martens hardness of 34 N / mm ² , and pencil hardness of H were confirmed to exhibit flexibility, restorability and hardness.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 11]
It replaced with the thermoplastic resin (A-2) and carried out similarly to Example 10 except having used the thermoplastic resin (A-3) and having set it as the polyfunctional thiol compound (D) of the ratio shown in Table 2.
The laminated sheet heat-cured by the same method as in Example 10 did not feel tacky and did not leave a fingerprint mark.
Furthermore, the laminated sheet obtained by curing under the same ultraviolet irradiation conditions as in Example 10 showed excellent transparency with a total light transmittance of 93% and a haze of 0.4%.
Moreover, since the thermoplastic resin (A-3), the inorganic fine particles (B), and the polyfunctional thiol compound (D) which are low Tg polymers and have side chains were used, the obtained resin had a restoration rate of 83 0.1%, indentation elastic modulus of 1238 MPa, Martens hardness of 69 N / mm ² , and pencil hardness of 2H, and it was confirmed that flexibility, restorability and hardness were exhibited.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 12]
Using “Biscoat # 230” (1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as the polyfunctional monomer (C), a resin composition (X ′ The procedure was the same as in Example 11 except that -12) was applied.
The laminated sheet heat-cured by the same method as in Example 11 had no tackiness and no fingerprints.
Furthermore, the laminated sheet obtained by curing under the same ultraviolet irradiation conditions as in Example 11 showed excellent transparency with a total light transmittance of 93% and a haze of 0.4%.
Moreover, since the thermoplastic resin (A-3), the inorganic fine particles (B), and the polyfunctional thiol compound (D) that are low Tg polymers and have side chains are used, the obtained resin has a restoration rate of 75. .9%, indentation elastic modulus of 1415 MPa, Martens hardness of 72 N / mm ² , and pencil hardness of 2H were confirmed to exhibit flexibility, resilience and hardness.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 13]
The same procedure as in Example 11 was performed except that the thermoplastic resin (A-3) and the thermoplastic resin (A-4) were used and the resin composition (X′-13) having the composition shown in Table 2 was used.
The laminated sheet heat-cured by the same method as in Example 11 had no tackiness and no fingerprints.
Furthermore, the laminated sheet obtained by curing under the same ultraviolet irradiation conditions as in Example 11 showed excellent transparency with a total light transmittance of 93% and a haze of 0.4%.
Further, since the thermoplastic resin (A-3) and the thermoplastic resin (A-4), the inorganic fine particles (B) and the polyfunctional thiol compound (D) having a low Tg polymer and having side chains are used, The obtained resin has a recovery rate of 80.4%, an indentation elastic modulus of 1160 MPa, a Martens hardness of 61 N / mm ² , and a pencil hardness of 2H, and is confirmed to exhibit flexibility, restorability and hardness. It was.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Example 14]
The same procedure as in Example 11 was performed except that the thermoplastic resin (A-3) and the thermoplastic resin (A-5) were used and the resin composition (X′-14) having the composition shown in Table 2 was used.
The laminated sheet heat-cured by the same method as in Example 11 had no tackiness and no fingerprints.
Furthermore, the laminated sheet obtained by curing under the same ultraviolet irradiation conditions as in Example 11 showed excellent transparency with a total light transmittance of 93% and a haze of 0.4%.
Further, since the thermoplastic resin (A-3) and the thermoplastic resin (A-5), the inorganic fine particles (B) and the polyfunctional thiol compound (D) having a low Tg polymer and having a side chain are used, The obtained resin has a restoration rate of 81.3%, an indentation elastic modulus of 1070 MPa, a Martens hardness of 58 N / mm ² , and a pencil hardness of 2H, and is confirmed to exhibit flexibility, restorability and hardness. It was.
In addition, even when scratched with a ballpoint pen, the restoration of the scratch was observed, so that it was possible to confirm a good restoration property against the wound.
The evaluation results of the laminated sheet are shown in Table 2.

[Comparative Example 1]
Except having obtained the layer of resin (X-15) as a resin composition (X'-15) of only a thermoplastic resin (A-1) and a photoinitiator (E), it carried out like Example 1. .
The obtained laminated sheet had a total light transmittance of 93% and a haze of 0.3%, and exhibited excellent transparency.
However, since only the thermoplastic resin (A-1) having a low Tg polymer and a side chain is used, the obtained resin has a restoration rate of 100%, an indentation elastic modulus of 86 MPa, and a Martens hardness of 5 Although it showed extremely excellent flexibility and resilience of 0.0 N / mm ² , the pencil hardness was only 5 B or less, indicating a very low hardness, and the resin did not satisfy all of flexibility, resilience and hardness. .
Further, when scratched with a ballpoint pen, the resin (X-15) layer was too soft, so that scratches were deep and did not appear to be restored.
The evaluation results of the laminated sheet are shown in Table 2.

[Comparative Example 2]
Instead of the thermoplastic resin (A-2), a thermoplastic resin (A-6) was used, and a resin composition (X-16) layer was obtained as a resin composition (X′-16) in the ratio shown in Table 2. Except for this, the same procedure as in Example 2 was performed.
The obtained laminated sheet had an excellent transparency with a total light transmittance of 92% and a haze of 0.5%.
However, since it is a hard layer composed only of the thermoplastic resin (A-6) having a side chain obtained from a polymer exhibiting a high Tg and the inorganic fine particles (B), the obtained resin has a restoration rate of 65.2. %, Indentation elastic modulus is 4500 MPa, Martens hardness is 250 N / mm ² , and pencil hardness is ² H. Although it shows high hardness, it is inferior in flexibility and resilience, and is a restoration rate that serves as a standard for scratches to be restored or inconspicuous 70% or more could not be secured.
When scratched with a ballpoint pen, the pencil hardness was high and scratches were difficult to be scratched, but no restoration of the scratches was found.
The evaluation results of the laminated sheet are shown in Table 2.

ＭＥＫ：メチルエチルケトン
ｎ−ＢＡ：ブチルアクリレート
ＭＭＡ：メチルメタクリレート
４ＨＢＡＧＥ：４−ヒドロキシブチルアクリレートグリシジルエーテル
ＧＭＡ：グリシジルメタクリレート
ＡＩＢＮ：アゾビスイソブチロニトリル
ＭＥＨＱ：ハイドロキノンモノメチルエーテル
ＴＰＰ：トリフェニルホスフィン
ＡＡ：アクリル酸

MEK: methyl ethyl ketone n-BA: butyl acrylate MMA: methyl methacrylate 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether GMA: glycidyl methacrylate AIBN: azobisisobutyronitrile MEHQ: hydroquinone monomethyl ether TPP: triphenylphosphine AA: acrylic acid

[Example 15]
Example 2 except that the resin composition (X′-2) was used, and a transparent soft acrylic resin sheet (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBS010P) containing a crosslinked rubber component as a substrate was used. In the same manner as above, a laminated film in which resin layers were laminated was obtained.
The resin (X-2) layer of the obtained film showed the same physical properties as in Example 2, and when the film was further bent, the resin (X-2) layer was flexible and thus cracked. It was confirmed that it was difficult to occur and excellent in handleability.

[Example 16]
Example 7 except that the resin composition (X′-7) was used and a transparent soft acrylic resin sheet (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBS010P) containing a crosslinked rubber component as a substrate was used. Application and drying were performed in the same manner as in Example 1 to obtain a laminated film in which a layer of the heat-cured resin (X-7) was laminated on the substrate.
Using this laminated film, it was placed in a mold having a vacuuming function so that the layer side of the resin (X-7) after thermosetting was on the cavity side, and heated with a heater until the laminated film reached 190 ° C. Thereafter, vacuum forming was performed. The shape of the laminated film after vacuum forming was a box shape having a length of 150 mm × width of 120 mm and a depth of 10 mm.
Since the layer of the resin (X-7) after thermosetting has excellent flexibility, no cracks are seen after vacuum forming, and the resin (X-7) to the mold is sufficiently cured. ) Was not observed.
Next, unnecessary portions of the vacuum-formed laminated film (portions that do not adhere to the substrate in the final laminated body) were trimmed from the layer side of the resin (X-7) using a Thomson punching die.
Subsequently, an ABS resin (UMG ABS Co., Ltd., trade name diamond, which is arranged so that the layer side of the resin (X-7) of the laminated film after vacuum forming that is trimmed is the cavity side and is melted on the substrate side. PET ABS “Bulksum TM25B”) was injected, and a molded body having a resin (X-7) layer as a surface layer was obtained by insert molding. The shape of the molded body was a box shape having a length of 150 mm, a width of 120 mm, a thickness of 2 mm, and a depth of 10 mm.
The resin (X-7) layer of the obtained molded body was cured under the same ultraviolet irradiation conditions as in Example 7, and the cured resin (X-7) layer was scratched with a ballpoint pen to restore the scratches. As a result, it was possible to obtain a molded article having good resilience against scratches.

  As described above, according to the present invention, it is possible to provide a resin that has a high hardness and is flexible and capable of restoring or making the scratch inconspicuous by its excellent restoring force even when scratched. Become. In addition, since the molded body and film using the resin have the above-mentioned characteristics, they can be suitably used for surface protection of various base materials, such as automotive interior members, automotive exterior members and other vehicle members, and architectural use. It can be used for many applications such as interior materials, building materials such as building exterior materials, various surface decorative materials, and optical members.

Claims (12)

Resin (X) whose restoration rate (x) and indentation elastic modulus measured by the nanoindentation method are as described in the following (i) and (ii), and whose pencil hardness is H or more ).
Measurement conditions A load is applied to the surface of the resin while gradually increasing the load to the Vickers indenter at 5 mN / 5 seconds. The load is unloaded while being held, and after unloading, hold for 25 seconds.
(I) The resin restoration rate (x) calculated from the following formula (1) is 70% or more and 100% or less.

Here, the restoration rate (x) is measured under the above measurement conditions, and Ls, Le, and Lmax used for the calculation are Ls: initial indentation depth when the load is started, Le: after unloading, and further, The indentation depth after being held for 25 seconds, Lmax: the indentation depth when the indenter was most deeply pushed in after being held at 5 mN for 10 seconds.
(Ii) The indentation elastic modulus is 10 MPa or more and 2000 MPa or less.   The resin composition for manufacturing resin (X) of Claim 1 containing the thermoplastic resin (A) which has a functional group which can be hardened | cured by an active energy ray in a side chain. A thermoplastic resin (A) having a functional group curable with active energy rays in the side chain is obtained by polymerizing the following monomer component (a), and the polymer having the following (iii) is converted into a radical: The resin composition according to claim 2, which is a polymer obtained by reacting a polymerizable unsaturated group and a monomer having a carboxyl group.
Monomer component (a)
-(Meth) acrylate (a-1) having an epoxy group 5 to 70% by mass
-(Meth) acrylate other than (a-1) (a-2) 95-30% by mass
-Monomer (a-3) copolymerizable with (a-1) and (a-2) 0 to 30% by mass
(Iii) Glass transition temperature (Tg) is 0 ° C. or lower.
Here, Tg is a value calculated from the FOX equation.   The resin composition according to claim 2 or 3, further comprising inorganic fine particles (B).   The resin composition according to any one of claims 2 to 4, further comprising a polyfunctional monomer (C).   6. The resin composition according to claim 5, wherein the polyfunctional monomer (C) is a polyfunctional monomer having two or more radical polymerizable functional groups and a polyalkylene glycol structure in one molecule.   The resin composition according to any one of claims 2 to 6, further comprising a polyfunctional thiol compound (D).   Resin (X) formed by curing the resin composition according to any one of claims 2 to 7 with active energy rays.   A resin (X) obtained by thermally curing the resin composition according to claim 7 and further curing with an active energy ray.   The laminated body which has the layer of resin (X) of Claim 1, or the cured resin (X) of Claims 8-9 on the at least one surface of a base material.   The laminate according to claim 10, wherein the substrate has a film shape.   A laminate having the resin composition layer according to claim 7 is heated, the resin composition layer is thermally cured, and then molded, and the resin composition layer is further cured by active energy rays. A molded article having a layer of resin (X).