JP7404656B2 - Curable resin compositions, cured resin products, laminated films, transfer films, and laminates - Google Patents

Description

The present disclosure relates to a curable resin composition, a resin cured product, a laminate film, a transfer film, and a laminate using the same.

Conventionally, polycarbonate, polyacrylate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyolefin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), etc. are known as resin materials for organic glass. It has excellent impact resistance, heat resistance, transparency, etc., and its use in windows of vehicles such as automobiles and buildings is being attempted.

When the above-mentioned organic glass resin material is used for applications such as the above-mentioned automobile windows, abrasion resistance is usually required. Therefore, in recent years, surface protective layers have been used to protect the surfaces of organic glasses. A hard coat film having a hard coat layer is used as a film for disposing such a surface protective layer on the surface of an article.

On the other hand, curable resin compositions that are cured by irradiation with active energy rays such as ultraviolet rays and electron beams harden to form cured products that have scratch resistance and chemical resistance, so they can be used to protect the surface of articles and improve designs. It is used in a wide range of applications, from paints and coating agents to impart properties to optical materials that provide optical properties when molded into a desired shape, and is also used as the hard coat layer mentioned above.

Furthermore, in recent years, insert molding, in which a protective film or decorative film with a surface protective layer on the base material is inserted into an injection mold, and the entire film is attached to the molded product, has been introduced. A protective film or decorative film with a layer on a base material is inserted into a mold, and after injection molding is performed, the base material is peeled off, leaving the surface protective layer and optionally a decorative layer on the molded product. Its use in mold transfer films is expanding.

Generally, a curable resin composition is cured to increase crosslink density to form a cured layer with improved surface hardness. However, since such a cured material layer has reduced flexibility and becomes brittle, it may crack when bent or stretched or easily break when subjected to an impact from an external force. Furthermore, when used in the above-mentioned insert molding or in-mold transfer film, there was a problem that the hardening of the surface protective layer lowered the elongation of the resin and deteriorated the processability.

As described above, in recent years, cured products of curable resin compositions for surface protection are required to have excellent elongation properties (hereinafter sometimes referred to as extensibility) while having high abrasion resistance. ing.

Patent Document 1 describes a compound having two or more ethylenically unsaturated groups and an isocyanurate ring ( Disclosed is a composition for a photocurable decorative laminated film, which comprises A) and a photopolymerization initiator (B) and has an ethylenically unsaturated group concentration of 0.1 to 4.0 meq/g. It is disclosed that the compound (A) has an oxyalkylene group or/and a group represented by -COC _N H _2N O- (N is an integer of 2 to 6). However, although the composition of the invention described above had excellent workability, it had insufficient wear resistance.

Japanese Patent Application Publication No. 2011-225679

In recent years, cured products of curable resin compositions for surface protection are required to have high abrasion resistance and excellent extensibility (tensile elongation) as described above. Furthermore, in resin glass with a hard coat layer for automobiles, cracks may occur in the hard coat layer during the process of cleaning the surface with a chemical such as ethanol. Therefore, the hard coat layer is required to have chemical resistance, especially ethanol resistance, in addition to abrasion resistance and extensibility.

The present disclosure has been made in view of the above circumstances, and its main purpose is to provide a curable resin composition capable of obtaining a cured product having excellent abrasion resistance, elongation properties, and chemical resistance. purpose.

This disclosure:
(A) a urethane compound that is a reaction product of a compound (a1) represented by the following general formula (1) and an isocyanate ring-containing isocyanate ring (a2) represented by the following general formula (2);
(B) a compound having an isocyanurate ring represented by the following general formula (3);
(C) inorganic particles having an average primary particle size of 10 nm to 100 nm;
Provided is a curable resin composition comprising:

（式中、Ｚ^１は、重合性炭素－炭素二重結合含有基である。Ｒ^１は、酸素原子を含んでも良い２価の炭化水素基である。Ｒ^２は、水素原子又は１価の炭化水素基である。Ｒ^３は、単結合又は２価の炭化水素基である。ｎは１～３の整数であり、ｍは１～３の整数であり、ｎ＋ｍは２～４を満たす数である。ｎが２以上のとき、２つ以上のＺ^１及びＲ^１は同一であっても異なってもよい。ｍが２以上のとき、２つ以上のＲ^３は同一であっても異なってもよい。４－ｎ－ｍが２のとき、２つのＲ^２は同一であっても異なってもよい。）

(In the formula, Z ¹ is a polymerizable carbon-carbon double bond-containing group. R ¹ is a divalent hydrocarbon group which may contain an oxygen atom. R ² is a hydrogen atom or a monovalent hydrocarbon group. It is a hydrocarbon group. R ³ is a single bond or a divalent hydrocarbon group. n is an integer of 1 to 3, m is an integer of 1 to 3, and n+m is a number satisfying 2 to 4. When n is 2 or more, two or more Z ¹ and R ¹ may be the same or different. When m is 2 or more, two or more R ³ may be the same or different. (When 4-nm is 2, the two ^R2s may be the same or different.)

（式中、Ｒ^４はそれぞれ独立に、同一又は異種の、酸素原子を含んでも良い２価の炭化水素基である。）

(In the formula, each R ⁴ is independently the same or different divalent hydrocarbon group which may contain an oxygen atom.)

（式中、Ｚ^２はそれぞれ独立に、同一又は異種の、重合性炭素－炭素二重結合含有基である。Ｒ^５はそれぞれ独立に、同一又は異種の、酸素原子を含んでも良い２価の炭化水素基である。）

(In the formula, Z ² is each independently the same or different type of polymerizable carbon-carbon double bond-containing group. R ⁵ is each independently the same or different type of divalent group which may contain an oxygen atom. It is a hydrocarbon group.)

By containing the components (A) and (B) having isocyanurate rings, the curable resin composition of the present disclosure can improve the balance between crosslink density and intermolecular cohesive force between isocyanurate rings. Therefore, it is possible to impart resistance to chemicals such as ethanol and methanol while maintaining extensibility to the cured product. Furthermore, hydrophobicity and extensibility can be imparted by the group between the isocyanurate ring and the polymerizable carbon-carbon double bond-containing group. Therefore, the cured product can be provided with excellent extensibility and resistance to highly polar chemicals such as ethanol and methanol. Furthermore, by including component (C), the cured product has excellent wear resistance.

In the present disclosure, the component (A) is a compound (in the general formula (1)) in which n is 3, m is 1, Z ¹ is a (meth)acryloyloxy group, and R ¹ and R ³ are methylene groups ( It is preferable that it is a reaction product of a1) and an isocyanate (a2) in which R ⁴ in the above general formula (2) is a linear, branched, or cyclic divalent aliphatic hydrocarbon group.

This is because when component (A) is such a compound, a cured product with good hydrophobicity and extensibility can be obtained.

In the present disclosure, in the above-mentioned component (B), Z ² in the above general formula (3) is a (meth)acryloyloxy group, and at least one of the three R ⁵ has 5 to 5 carbon atoms including an ester group. A compound having 15 divalent aliphatic hydrocarbon groups is preferable.

This is because if such component (B) is used, hydrophobicity is improved and a cured product with better chemical resistance can be obtained.

The curable resin composition of the present disclosure preferably further contains a reaction product of the compound represented by the above general formula (1) and an isocyanate that does not contain an isocyanurate structure and has an alicyclic structure.

This is because, by including a urethanization reaction product different from component (A), the cured product has even better extensibility.

Further, the present disclosure provides a cured resin product that is a cured product of the above-mentioned curable resin composition.
The cured resin product of the present disclosure has excellent abrasion resistance, elongation properties, and chemical resistance.
The present disclosure provides a laminated film having a cured resin layer, which is the above-mentioned cured resin layer, on a base layer.

The present disclosure is a transfer film having a transfer base material layer and a hard coat layer laminated on the transfer base material layer, wherein the hard coat layer is a cured product of the above-mentioned curable resin composition. A transfer film is provided.

The present disclosure provides a laminate having a resin base and a hard coat layer laminated on the resin base, wherein either a primer layer or an adhesive layer is provided between the resin base and the hard coat layer. or both, and the hard coat layer provides a laminate that is a cured product of the above-mentioned curable resin composition.

The hard coat layer, which is the cured product layer of the curable resin composition of the present disclosure, can provide a cured product with chemical resistance, so even if the primer layer or adhesive layer has low chemical resistance, the laminate It is possible to improve the chemical resistance of

The curable resin composition of the present disclosure has the effect that a cured product having excellent abrasion resistance, processability (extensibility), and chemical resistance can be obtained.

FIG. 1 is a schematic cross-sectional view showing an example of a laminated film of the present disclosure. FIG. 1 is a schematic cross-sectional view showing an example of a transfer film of the present disclosure. FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present disclosure. It is a schematic sectional view showing another example (laminate film) of a laminated film of this indication. FIG. 3 is a schematic cross-sectional view showing another example of the laminate of the present disclosure.

In order to solve the above problems, the present inventors conducted intensive studies and found that even if the hydrophobicity is increased using an aliphatic compound, elongation and abrasion resistance can be imparted to the cured product, but chemical resistance cannot be imparted. I found out that it is not possible. On the other hand, if the chemical resistance is improved by increasing the crosslinking density, the extensibility will be reduced. Therefore, by using two or more specific organic compounds that have isocyanurate rings, we are able to achieve a balance between the concentration of isocyanurate rings in the cured product and an appropriate crosslinking density, thereby curing without impairing extensibility. This makes it possible to improve the chemical resistance (especially ethanol resistance) of objects. In other words, it is assumed that the chemical resistance is improved by improving the intermolecular cohesive force of the isocyanurate ring, and that the bond due to the intermolecular cohesive force of the isocyanurate ring is relatively easy to attach and detach. This is because it is estimated that excellent extensibility can be obtained by this. Furthermore, it has been found that wear resistance can be achieved by including inorganic particles.

Hereinafter, the curable resin composition, cured resin product, laminate film, transfer film, and laminate of the present disclosure will be described in detail.
In this specification, (meth)acrylic represents each of acrylic and methacrylic, (meth)acryloyl represents each of acryloyl and methacryloyl, and (meth)acrylate represents each of acrylate and methacrylate.

Note that the present disclosure can be implemented in many different embodiments, and should not be interpreted as being limited to the contents of the embodiments exemplified below. In addition, in order to make the explanation clearer, the drawings may schematically represent the width, thickness, shape, etc. of each member compared to the embodiment, but this is only an example, and the interpretation of this disclosure is It is not limited to. In addition, in this specification and each figure, the same elements as those described above with respect to the previously shown figures are denoted by the same reference numerals, and detailed explanations may be omitted as appropriate.

In this specification, when expressing a mode in which another member is placed on top of a certain member, when it is simply expressed as "above" or "below", unless otherwise specified, it means that the member is in contact with a certain member. This includes both cases in which another member is placed directly above or below a certain member, and cases in which another member is placed above or below a certain member via another member. In addition, in this specification, when expressing the aspect of arranging another member on top of a certain member, when it is simply expressed as “on a surface”, unless otherwise specified, it means directly above or in contact with a certain member. This includes both a case where another member is placed directly below a certain member and a case where another member is placed above or below a certain member via another member.

I. Curable resin composition The curable resin composition of the present disclosure includes:
(A) a urethane compound that is a reaction product of a compound (a1) represented by the following general formula (1) and an isocyanate ring-containing isocyanate ring (a2) represented by the following general formula (2);
(B) a compound having an isocyanurate ring represented by the following general formula (3);
(C) inorganic particles having an average primary particle size of 10 nm to 100 nm;
A curable resin composition comprising:

（式中、Ｚ^１は、重合性炭素－炭素二重結合含有基である。Ｒ^１は、酸素原子を含んでも良い２価の炭化水素基である。Ｒ^２は、水素原子又は１価の炭化水素基である。Ｒ^３は、単結合又は２価の炭化水素基である。ｎは１～３の整数であり、ｍは１～３の整数であり、ｎ＋ｍは２～４を満たす数である。ｎが２以上のとき、２つ以上のＺ^１及びＲ^１は同一であっても異なってもよい。ｍが２以上のとき、２つ以上のＲ^３は同一であっても異なってもよい。４－ｎ－ｍが２のとき、２つのＲ^２は同一であっても異なってもよい）

(In the formula, Z ¹ is a polymerizable carbon-carbon double bond-containing group. R ¹ is a divalent hydrocarbon group which may contain an oxygen atom. R ² is a hydrogen atom or a monovalent hydrocarbon group. It is a hydrocarbon group. R ³ is a single bond or a divalent hydrocarbon group. n is an integer of 1 to 3, m is an integer of 1 to 3, and n+m is a number satisfying 2 to 4. When n is 2 or more, two or more Z ¹ and R ¹ may be the same or different. When m is 2 or more, two or more R ³ may be the same or different. (When 4-nm is 2, the two ^R2s may be the same or different)

（式中、Ｒ^４はそれぞれ独立に、同一又は異種の、酸素原子を含んでも良い２価の炭化水素基である。）

(In the formula, each R ⁴ is independently the same or different divalent hydrocarbon group which may contain an oxygen atom.)

（式中、Ｚ^２はそれぞれ独立に、同一又は異種の、重合性炭素－炭素二重結合含有基である。Ｒ^５はそれぞれ独立に、同一又は異種の、酸素原子を含んでも良い２価の炭化水素基である。）

(In the formula, Z ² is each independently the same or different type of polymerizable carbon-carbon double bond-containing group. R ⁵ is each independently the same or different type of divalent group which may contain an oxygen atom. It is a hydrocarbon group.)

The curable resin composition of the present disclosure can improve intermolecular cohesive force by containing the above components (A) and (B) having an isocyanurate ring. Furthermore, hydrophobicity can be imparted by a group between the isocyanurate ring and the polymerizable carbon-carbon double bond-containing group. Therefore, it is possible to impart excellent extensibility to the cured product and resistance to highly polar chemicals such as ethanol and methanol. Furthermore, by including component (C), the cured product has excellent wear resistance. If only component (A) is present, the chemical resistance due to the intermolecular cohesive force between the isocyanurate rings in the composition will be insufficient, but by including component (B), this will be compensated for and the cured product will have excellent properties. It can provide stretchability and chemical resistance.

A. Urethane compound (A)
The urethane compound (A) used in the curable resin composition of the present disclosure includes a compound (a1) represented by the following general formula (1) and an isocyanate (a2) having an isocyanurate ring represented by the following general formula (2). ) is a reaction product with

（式中、Ｚ^１は、重合性炭素－炭素二重結合含有基である。Ｒ^１は、酸素原子を含んでも良い２価の炭化水素基である。Ｒ^２は、水素原子又は１価の炭化水素基である。Ｒ^３は、単結合又は２価の炭化水素基である。ｎは１～３の整数であり、ｍは１～３の整数であり、ｎ＋ｍは２～４を満たす数である。ｎが２以上のとき、２つ以上のＺ^１及びＲ^１は同一であっても異なってもよい。ｍが２以上のとき、２つ以上のＲ^３は同一であっても異なってもよい。４－ｎ－ｍが２のとき、２つのＲ^２は同一であっても異なってもよい。）

(In the formula, Z ¹ is a polymerizable carbon-carbon double bond-containing group. R ¹ is a divalent hydrocarbon group which may contain an oxygen atom. R ² is a hydrogen atom or a monovalent hydrocarbon group. It is a hydrocarbon group. R ³ is a single bond or a divalent hydrocarbon group. n is an integer of 1 to 3, m is an integer of 1 to 3, and n+m is a number satisfying 2 to 4. When n is 2 or more, two or more Z ¹ and R ¹ may be the same or different. When m is 2 or more, two or more R ³ may be the same or different. (When 4-nm is 2, the two ^R2s may be the same or different.)

（式中、Ｒ^４はそれぞれ独立に、同一又は異種の、酸素原子を含んでも良い２価の炭化水素基である。）

(In the formula, each R ⁴ is independently the same or different divalent hydrocarbon group which may contain an oxygen atom.)

1. Compound (a1) represented by general formula (1)
In the compound (a1) represented by the above general formula (1), Z ¹ is a group containing a polymerizable carbon-carbon double bond.
The polymerizable carbon-carbon double bond-containing group is not particularly limited as long as it contains a polymerizable carbon-carbon double bond, but examples include vinyl group, (meth)acryloyl group, and (meth)acryloyl group. Examples include oxy group and allyl group. When n is 2 or more (ie, 2 or 3), two or three Z ¹ 's may be the same or different.

R ¹ is a divalent hydrocarbon group that may contain an oxygen atom, such as a linear, branched, or cyclic divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms; Examples include groups containing one or more ether bonds, ester bonds, carbonyl groups, etc. between carbon-carbon bonds of a hydrocarbon group. Preferably, it is a linear alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group, ethylene group, or propylene group. When n is 2 or more (ie, 2 or 3), two or three R ¹ 's may be the same or different.

R ² is a hydrogen atom or a monovalent hydrocarbon group, preferably a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom or It is a methyl group. When 4-nm is 2, the two R ² 's may be the same or different.

R ³ is a single bond or a divalent hydrocarbon group, preferably a single bond or a linear, branched, or cyclic alkylene group having 1 to 3 carbon atoms, particularly preferably a single bond or It is a methylene group. When m is 2 or more (ie, 2 or 3), two or three R ³ 's may be the same or different.

n is an integer from 1 to 3, m is an integer from 1 to 3, and n+m is a number satisfying 2 to 4. That is, the combination of n and m is (n, m) = (1, 1), (1, 2), (2, 1), (3, 1), (2, 2) or (1, 3) It is.

The compound (a1) is pentaerythritol modified with (meth)acrylic acid, that is, one, two, or three of the four hydroxyl groups contained in pentaerythritol are (meth)acrylic acid. Preferably, it is a reaction product. One hydroxy group reacted with (meth)acrylic acid is pentaerythritol monoacrylate, n = 1, m = 3, Z ¹ = (meth)acryloyloxy group, R ¹ and R ³ are methylene groups . What two hydroxy groups reacted with (meth)acrylic acid is pentaerythritol diacrylate, n = 2, m = 2, Z ¹ = (meth)acryloyloxy group, R ¹ and R ³ are methylene groups . Pentaerythritol triacrylate (PETA) is obtained by reacting three hydroxy groups with (meth)acrylic acid, n=3, m=1, Z ¹ = (meth)acryloyloxy group, R ¹ and R ³ are methylene It is the basis.

In particular, compound (a1) is preferably composed mainly of pentaerythritol triacrylate (PETA) in which three hydroxyl groups in pentaerythritol are modified with (meth)acrylic acid. This means that if the quantitative ratio of pentaerythritol monoacrylate or pentaerythritol diacrylate is large, the reactant urethane Compound (A) may polymerize, which may reduce the dispersibility of the urethane compound (A) as a reactant and the compound (B) described below, which may adversely affect various physical properties. Because there is.
Therefore, the main component of compound (a1) is a compound in the above general formula (1) in which n is 3, m is 1, Z ¹ is a (meth)acryloyloxy group, and R ¹ and R ³ are methylene groups. That's preferable.
Here, the term "main component" means that, as mentioned above, pentaerythritol monoacrylate and pentaerythritol diacrylate are contained to the extent that the urethane compound (A) does not polymerize and does not adversely affect various physical properties. also means good.
In addition, the said compound (a1) may be used individually and may use 2 or more types together.

Furthermore, 2-hydroxypropyl acrylate (HPA) is also preferred as compound (a1). In this case, n=1, m=1, Z ¹ =(meth)acryloyloxy group, R ¹ and R ³ are methylene groups, and two R ² are a hydrogen atom and a methyl group.

2. Isocyanate (a2) having an isocyanurate ring represented by general formula (2)
In general formula (2), R ⁴ are each independently the same or different divalent hydrocarbon groups which may contain an oxygen atom.
The above R ⁴ includes, for example, a linear, branched, or cyclic divalent aliphatic hydrocarbon group having 6 to 13 carbon atoms, one or more ether bonds, ester bonds, or carbonyl groups. Examples include divalent aliphatic hydrocarbon groups having 7 to 13 carbon atoms.

In this way, when R ⁴ is an isocyanate (a2) which is an aliphatic hydrocarbon group having a predetermined number of carbon atoms, it is possible to obtain a cured product with good extensibility and excellent workability when made into a cured product. can. Furthermore, by imparting hydrophobicity, a cured product with excellent chemical resistance can be obtained. Furthermore, since the mobility of isocyanurate rings within the cured product can be improved, it is estimated that the bonding between isocyanurate rings due to intermolecular cohesive force can be improved.
Among these, an alkylene group having 6 to 8 carbon atoms is preferred, and a hexylene group and a cyclohexylene group are particularly preferred.

Isocyanates having such an isocyanurate ring are derived from diisocyanates having two isocyanate groups in the molecule. The above diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 1, Examples include diisocyanates such as 3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, and lysine diisocyanate, with hexamethylene diisocyanate and isophorone diisocyanate being particularly preferred.

3. Others The urethane compound (A) of the present disclosure is obtained by urethanizing the compound (a1) represented by the above general formula (1) and the isocyanate (a2) having an isocyanurate ring represented by the above general formula (2). This is a compound obtained by In particular, the compound (a1) in which n in the general formula (1) is 3, m is 1, Z ¹ is a (meth)acryloyloxy group, and R ¹ and R ³ are methylene groups; ) in which R ⁴ is preferably a reaction product with isocyanate (a2) which is a linear, branched, or cyclic divalent aliphatic hydrocarbon group.

The method for obtaining the urethane compound (A) is not particularly limited, and it can be produced according to generally known methods. For example, in a reaction vessel, the compound (a1) represented by the above general formula (1), the isocyanate (a2) having an isocyanurate ring represented by the above general formula (2), and optionally a urethanization catalyst, polymerization An inhibitor and an organic solvent are added, and a predetermined temperature is maintained for reaction.

The reaction ratio of each component is such that the hydroxyl group contained in the compound (a1) represented by the above general formula (1) and the isocyanate ring-containing isocyanurate ring represented by the above general formula (2) are equivalent. Although it is preferable to carry out the reaction, during production, the reaction is carried out at an equivalent ratio of hydroxyl group/isocyanate group usually in the range of 0.8 to 1.1.

Note that the isocyanate (a2) and the compound (a1) may be reacted by adding one of the raw materials in advance and then dropping a raw material other than the raw material that was previously supplied. Further, the urethanization reaction is usually carried out at a temperature in the range of 60 to 120°C. The end point of the urethanization reaction can be confirmed by the disappearance of the infrared absorption spectrum at 2270 cm ^-1 indicating isocyanate groups or by determining the content of isocyanate groups by the method described in JIS K 7301. As the urethanization catalyst, a tin compound such as dibutyltin dilaurate or an amine such as triethylamine can be used.

Regarding the molecular weight of the urethane compound (A), the weight average molecular weight is 1,000 or more and 25,000 or more in order to improve the dispersibility of the urethane compound (A) as a reactant and the compound (B) described below and to achieve uniform physical properties. It is preferable that it is below.

Here, the weight average molecular weight (Mw) in this specification is determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
For example, the measuring device used was GPC HLC-8220 manufactured by Tosoh Corporation, two Shodex LF-404 columns were connected in series, a differential refractive index (RI) detector was used as the detector, and an Agilent standard polystyrene was used as the detector. Easical Type PS-2 polystyrene manufactured by Technologies (molecular weight range 580-364,000) can be used.

The amount of the urethane compound (A) in the curable resin composition of the present disclosure is not particularly limited, but is within the range of 18 parts by mass to 60 parts by mass, particularly 36 parts by mass based on 100 parts by mass of solid content of the curable resin composition. It is preferably within the range of 54 parts to 54 parts by weight. This is because various physical properties required for the cured product can be obtained.
In addition, when blending the urethane compound (A) and the urethane compound (D) shown in "D. Other components" described later, the urethane compound (A) and the urethane compound (D) described later are mixed together. ) is within the range of 10 parts by mass to 90 parts by mass, particularly within the range of 20 parts by mass to 70 parts by mass, based on 100 parts by mass of the solid content of the curable resin composition. This is preferable because it can further improve various physical properties required for.

B. Compound (B) having an isocyanurate ring
Component (B) in the present disclosure is a compound having an isocyanurate ring represented by the following general formula (3).

（式中、Ｚ^２はそれぞれ独立に、同一又は異種の、重合性炭素－炭素二重結合含有基である。Ｒ^５はそれぞれ独立に、同一又は異種の、酸素原子を含んでも良い２価の炭化水素基である。）

(In the formula, Z ² is each independently the same or different type of polymerizable carbon-carbon double bond-containing group. R ⁵ is each independently the same or different type of divalent group which may contain an oxygen atom. It is a hydrocarbon group.)

By adding component (B), the balance between the crosslinking density and the isocyanurate ring density of the cured product can be improved, and chemical resistance can be improved without impairing extensibility. be able to.

In the above general formula (3), Z ² are each independently the same or different groups containing a polymerizable carbon-carbon double bond.
Further, examples of the polymerizable carbon-carbon double bond-containing group include the same groups as those exemplified for Z ¹ in the general formula (1). In particular, from the viewpoint of polymerizability, a (meth)acryloyl group and a (meth)acryloyloxy group are preferred.

R ⁵ is each independently the same or different divalent hydrocarbon group which may contain an oxygen atom, but is preferably an alkylene group having 2 to 7 carbon atoms, or an alkylene group having 5 to 7 carbon atoms containing an ester group. 15 divalent aliphatic hydrocarbon groups are preferred. By making it hydrophobic, it is possible to improve alcohol resistance and improve the mobility of isocyanurate rings within the cured product, which improves the bonding between isocyanurate rings due to intermolecular cohesive force. This is because it is presumed that it is possible.
In the present disclosure, it is particularly preferable to use a compound in which at least one of the three R ⁵ groups is a divalent aliphatic hydrocarbon group having 5 to 15 carbon atoms and containing an ester group. In this case, the other R ⁵ is preferably a linear alkylene group having 2 to 7 carbon atoms.

The compound in which at least one of the three R ⁵ is a divalent aliphatic hydrocarbon group having 5 to 15 carbon atoms containing an ester group may be selected as appropriate and commercially available products may be used, such as the following: Examples include ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate (NK Ester A9300-1CL, NK Ester A9300-3CL (manufactured by Shin Nakamura Chemical Industries)) shown by the formula. Further, other (B) components include tris-(2-acryloxyethyl) isocyanurate (NK Ester A9300 (manufactured by Shin Nakamura Chemical Co., Ltd.)) which is not modified with ε-caprolactone and is represented by the following formula.

A9300-1CL

A9300-3CL

A9300

Further, a compound in which at least one of the three R ⁵ is a divalent aliphatic hydrocarbon group having 5 to 15 carbon atoms containing an ester group is a trishydroxyalkyl isocyanurate having a hydroxy group (for example, It can be synthesized in two steps: adding ε-caprolactone to (trishydroxyethyl isocyanurate) and then adding acrylic acid.

The amount of compound (B) is not particularly limited, but it should be within the range of 36 parts by mass to 82 parts by mass, particularly within the range of 46 parts by mass to 72 parts by mass, based on 100 parts by mass of solid content of the curable resin composition. However, it can be said that this is a preferable range in order to obtain various physical properties required for the cured product.

C. Inorganic particles (C)
Component (C) in the present disclosure is an inorganic particle having an average primary particle size of 10 nm to 100 nm. Preferred examples of inorganic particles include inorganic particles made of silica (colloidal silica, fumed silica, precipitated silica, etc.), alumina, zirconia, titania, metal oxides such as zinc oxide, etc., and have excellent transparency and wear resistance. From the viewpoint of improving the properties, inorganic particles made of silica or alumina are preferable. The shape of the particles may be spherical, ellipsoidal, polyhedral, scale-like, etc., and is not particularly limited, but spherical is preferable because it increases the hardness and provides excellent hard coat properties.

The inorganic particles may be non-reactive or may be reactive inorganic particles having a reactive functional group on the surface. Preferred examples of the reactive functional group include a vinyl group, (meth)acryloyl group, allyl group, epoxy group, and silanol group. Acryloyl group and allyl group are more preferred.

The inorganic particles of component (C) in the present disclosure having an average primary particle size of 10 nm to 100 nm may form a group of connected and agglomerated inorganic particles (unusual inorganic particles) with an average number of connections of 2 to 20. Connected aggregations may be regular or irregular.
Further, the irregularly shaped inorganic particles may have a reactive functional group on the surface. Preferred examples of the reactive functional group include a vinyl group, (meth)acryloyl group, allyl group, epoxy group, and silanol group.

In the curable resin composition of the present disclosure, the amount of component (C) is not particularly limited, but is within the range of 5 parts by mass to 20 parts by mass, particularly 10 parts by mass, based on 100 parts by mass of solid content of the curable resin composition. A content in the range of 15 parts by mass is preferred because excellent wear resistance can be reliably obtained.

D. Other components The curable resin composition of the present disclosure further includes a urethane compound (D ) is preferable. Examples of such isocyanates that do not contain an isocyanurate structure and have an alicyclic structure include isophorone diisocyanate (IPDI) and the like.
Including a urethane-forming reactant different from component (A) in this manner is preferable because it provides a cured product with even better elongation properties.

The curable resin composition of the present disclosure may also contain a solvent in order to adjust the viscosity of the composition and improve the smoothness, uniformity, and adhesion of the cured film to the object to be coated. . Known solvents can be used, such as alcohols such as ethanol, propanol, isopropanol, and butanol, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl. Examples include ketones such as isobutylketone, ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-ethoxypropanol, 2-(2-ethoxyethoxy)ethanol, 1,4-dioxane, and tetrahydrofuran. Two or more types of solvents may be used in combination.

In the curable resin composition of the present disclosure, the content ratio of the solvent is not particularly limited as long as it can be adjusted as appropriate depending on the purpose, but it is 25 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the curable resin composition. The content is preferably 30 parts by mass or more and 50 parts by mass or less.

In addition, when the curable resin composition of the present disclosure is ultraviolet curable using ultraviolet light for curing, in order to cure quickly, the composition of the present disclosure may include a photopolymerization initiator, a polymerization accelerator, a photoinitiation aid, etc. Agents etc. may be added. As the photopolymerization initiator, known ones can be used, such as acetophenone compounds, benzoin ether compounds, benzophenone compounds, thioxanthone compounds, and the like. Further, as the polymerization accelerator and photoinitiation aid, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, etc. can be used.
In addition, in the case of electron beam curing using an electron beam for curing, there is no need to add a photopolymerization initiator, a polymerization accelerator, a photoinitiation aid, etc. In this case, the content ratio of the urethane compound (A) and the compound (B) in the solid content can be increased, which is preferable since it is easy to improve the abrasion resistance and tensile elongation property.

Further, the curable resin composition of the present disclosure may further contain, as necessary, for example, a light stabilizer, an antioxidant, a plasticizer, a flame retardant, a surfactant, a leveling agent, a thermal polymerization inhibitor, an antistatic agent, Various additives such as antifogging agents, antibacterial agents, fillers, pigments, dyes, and coloring agents can be included.

E. Others The curable resin composition of the present disclosure is prepared by blending a urethane compound (A), the above-mentioned compound (B), inorganic particles (C), and various additives and solvents as necessary in predetermined proportions, and by a conventional method. It can be obtained by uniformly mixing.

II. Cured Resin Product The present disclosure provides a cured resin product that is a cured product of the above-mentioned curable resin composition.
The cured product of the curable resin composition of the present disclosure can be obtained by coating the above-mentioned curable resin composition of the present disclosure on a substrate to a desired thickness, and if desired using a solvent, drying to remove the solvent. It can be manufactured by removing it and then curing it by irradiating it with active energy rays. The cured resin product of the present disclosure has excellent abrasion resistance, elongation properties, and chemical resistance.

The method for coating the curable resin composition on the substrate is not particularly limited, and any known method can be applied as appropriate. Examples of coating methods include dipping method, flow coating method, spray method, spin coating method, gravure coating method, microgravure coating method, die coating method, slit reverse method, roll coating method, blade coating method, air knife coating method, Coating can also be done by any method such as an offset method or a bar coating method. Further, it can also be coated in an imagewise manner by printing methods such as gravure printing, gravure offset printing, and screen printing.

The coating amount may be appropriately selected depending on the purpose of the cured product and is not particularly limited. For example, when the purpose is a glass substitute, the thickness of the cured material layer cured by irradiation with active energy rays is 2 μm or more and 20 μm or less, preferably 3 μm or more and 15 μm or less, and more preferably 4 μm or more and 10 μm or less. Coating is preferred.

In order to evaporate the solvent added to the curable resin composition of the present disclosure as appropriate and necessary, known drying methods such as hot air heating, infrared heating, far infrared heating, etc. can be appropriately employed.
The preferable range of drying conditions varies depending on the boiling point of the solvent, the material of the base material, the amount of coating, etc., but in general, drying is carried out at a temperature of 60°C or higher and 180°C or lower for 10 seconds or more and 30 minutes or less. It will be done.

Active energy rays include ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps, electron beams extracted from particle accelerators of usually 20 to 2000 kV, and α. rays, β rays, γ rays, etc. can be used.

The cured product of the curable resin composition of the present disclosure can be suitably used for various optical products, various display members, automotive interior and exterior parts, wallpaper, furniture, various residential parts used for window glass, and the like.

III. Laminated Film The present disclosure provides a laminated film having a cured resin layer, which is the layer of the above-mentioned cured resin, on a base layer. FIG. 1 is a schematic cross-sectional view showing an example of the laminated film of the present disclosure.
As shown in FIG. 1, the laminated film 10 of the present disclosure has a structure in which a cured resin layer 2 of the curable resin composition of the present disclosure is provided on a base layer 1.

The cured product layer of the curable resin composition of the present disclosure has excellent wear resistance. The surface of the cured layer of the curable resin composition of the present disclosure was subjected to a Taber abrasion test using a wear wheel CS-10F, a load of 500 g, and a rotation speed of 500 revolutions according to JIS K7105, and the difference in haze value before and after the test was determined by ΔH%. When measured, ΔH% is preferably less than 10.0%, more preferably less than 8.0%.

The cured product layer of the curable resin composition of the present disclosure has excellent tensile elongation properties. The cured product layer of the curable resin composition of the present disclosure was subjected to a tensile test using a tensile tester (AUTOGRAPH AG-X manufactured by Shimadzu Corporation) at a distance between chucks of 5 cm and a pulling speed of 50 mm/min. The length of elongation when a crack occurs in the layer is measured and the elongation is determined as follows. The elongation is preferably 25% or more, more preferably 30% or more, and 35% or more. % or more is even more preferable.
Elongation = (length of elongation when cracks occur in the cured material layer) / (length of cured material layer before test) x 100 (%)

The laminated film 10 of the present disclosure may further include another layer depending on its usage. As will be described in detail below, the mode of use can be roughly divided into a transfer film for transferring a cured resin layer and a laminate film for pasting the entire film.

A. Transfer Film The present disclosure provides a transfer film having a base material layer for transcription and a hard coat layer laminated on the base material layer, wherein the hard coat layer is formed by curing the above-mentioned curable resin composition. We provide a transfer film that is a product. FIG. 2 is a schematic cross-sectional view showing an example of the transfer film of the present disclosure.
The transfer film 10 of the present disclosure shown in FIG. 2 has a transfer base material layer 1 and a hard coat layer 2 which is a cured product layer of the curable resin composition of the present disclosure, and further includes a hard coat layer 2. A primer layer 3 and an adhesive layer 4 are provided on top in this order.
Further, although not shown, the transfer film of the present disclosure may include a hard coat layer and a primer layer in this order on the base layer. Furthermore, the transfer film of the present disclosure may further include a layer other than the adhesive layer and the primer layer, such as a decorative layer. As another layer such as a decoration layer, a known layer can be appropriately selected and used.

The transfer film 10 of the present disclosure shown in FIG. The hard coat film of this embodiment, excluding the layer, can be transferred and pasted onto an adherend via the adhesive layer 4. Further, as long as the primer layer 3 has adhesive properties to the hard coat layer 2 and the adherend, the adhesive layer 4 may not be provided. Furthermore, the transfer film of the present disclosure can be transferred and pasted onto an adherend using the decoration layer without providing the adhesive layer 4, when the decoration layer has an adhesion function with the adherend. There may be.

According to this transfer film, when the adhesive layer 4 side is attached to the resin substrate 21 to form a laminate 20, the primer layer 3 or the adhesive layer 4, or both. The thermoplastic resin contained in the primer layer 3 and the adhesive layer 4 often has low resistance to chemicals such as ethanol, but even when such a layer with low chemical resistance exists, the curable resin of the present disclosure Since the hard coat layer, which is a cured product layer of the composition, has chemical resistance, it can improve the chemical resistance of the laminate.
Although the transfer film of the present disclosure can be used in various ways, it is particularly preferably used in a thermal transfer method or an in-mold molding method. In other words, the transfer film is preferably used for thermal transfer method or in-mold molding method.

Each structure of the transfer film of the present disclosure will be described below.
1. Base Material Layer The transfer base layer in the transfer film of the present disclosure is a member that is peeled off when transferring the hard coat layer of the present disclosure to a resin substrate.
The base material layer is not particularly limited, and those used as release layers of general transfer films can be used. Examples include resin films such as polyester resin films and polyolefin resin films.
The above-mentioned base material layer can be set as appropriate, regardless of whether it is transparent or not, and whether or not it is colored.

The surface of the base material layer on the hard coat layer side may be subjected to a known mold release treatment, or may be provided with a mold release layer such as a silicone resin. This is because the base material layer and the hard coat layer can be easily separated.
The base material layer may have a single layer structure or a multilayer structure. In the case of a multilayer structure, the thickness of the entire multilayer structure can be within the above range.

2. Hard Coat Layer The hard coat layer is a cured product of the above-mentioned curable resin composition. The curable resin composition and the cured product have been described in detail in the sections "I. Curable resin composition" and "II. Cured resin product" above, so their explanation will be omitted here.

3. Primer Layer A primer layer may be further provided when the adhesiveness between the cured product layer of the curable resin composition of the present disclosure and another layer such as the adhesive layer is insufficient.
Examples of materials that can be used for the primer layer include, but are not limited to, acrylic resins, urethane resins, vinyl chloride vinyl acetate copolymer resins, polyester resins, and chlorinated polyolefin resins. Further, the primer layer may contain additives that may be included in the above-mentioned curable resin composition of the present disclosure.
The thickness of the primer layer is not particularly limited, but may be, for example, 0.1 μm or more and 10 μm or less, preferably 1 μm or more and 5 μm or less.

4. Adhesive Layer The transfer film of the present disclosure can be provided with an adhesive layer on the outermost layer on the side opposite to the surface on the base layer side. In this embodiment, the adhesive layer has heat-sealability, so that the hard coat film of this embodiment can be transferred and attached to the resin substrate via the adhesive layer. Note that heat-sealability refers to the property of being able to adhere to an adherend by heating under desired conditions and melting the resin contained in the adhesive layer.

When the adhesive layer has heat-sealability, that is, when it is a heat-sealing layer, the adhesive layer contains a thermoplastic resin that can be welded by heat. The thermoplastic resin is not particularly limited, and includes, for example, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin, chlorinated polypropylene, chlorinated rubber, urethane resin, epoxy resin, styrene resin, etc. be able to. The above resins may be used alone or in combination of two or more.

The thickness of the adhesive layer is not particularly limited, but can be appropriately set so as to provide sufficient adhesive force when attaching the transfer film of this embodiment to a resin substrate. The thickness can be, for example, 1 μm or more and 7 μm or less, preferably 1 μm or more and 6 μm or less.

5. Decorative Layer When a decorative layer is further provided in this embodiment, the decorative layer is typically arranged on the side opposite to the hard coat layer 2 of the primer layer 3 in FIG.

The decoration layer includes a colorant and a binder resin. The binder resin contained in the decoration layer is not particularly limited, and may be a resin used in general decoration layers. Examples of the resin include polyvinyl resin, polyester resin, acrylic resin, polyvinyl acetal resin, cellulose resin, and the like.

Moreover, the coloring agent contained in the above-mentioned decoration layer is not particularly limited, and can be a known coloring agent used in general decoration layers. Examples of the coloring agent include inorganic pigments such as carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, Bengara, cadmium red, ultramarine blue, and cobalt blue, azo pigments, phthalocyanine pigments, anthraquinone pigments, Examples include perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine azo-based, dictopyrrolopyrrole-based, and isoindoline-based organic pigments or dyes.

The decoration layer may be arranged on a part of the surface of the primer layer opposite to the hard coat layer, or may be arranged on the entire surface. Further, the decorative layer may be in a non-patterned form that covers the entire surface of the primer layer opposite to the hard coat layer, and the decorative layer may cover the entire surface of the primer layer opposite to the hard coat layer. It may be a pattern in which a placement area and a non-placement area occur. Further, the patterned decorative layer may represent a desired design. The above-mentioned design is not particularly limited, and may be, for example, a pattern or picture of characters, figures, symbols, etc.
The decoration layer may be transparent, translucent, or opaque.

The thickness of the decorative layer is not particularly limited, but can be, for example, 5 μm or more and 40 μm or less, preferably 5 μm or more and 30 μm or less.
In the transfer film of this embodiment, when a decorative layer is provided, the decorative layer and the adhesive layer may be formed separately, but the decorative layer and the adhesive layer may be formed integrally. It's okay. A single layer in which the decoration layer and the adhesive layer are integrally formed can serve as the decoration layer and the adhesive layer. The decoration layer/adhesive layer can exhibit both the function as a decoration layer and the adhesive function, for example, when the decoration layer contains a heat-weldable thermoplastic resin.

6. Manufacturing method The method for manufacturing the transfer film of the present disclosure is not particularly limited, but includes at least the step of, for example, applying and curing a composition for forming a hard coat layer on a transfer base layer to form a hard coat layer. When manufacturing the transfer film of the embodiment shown in Figure 2, a primer composition is applied on the hard coat layer, cured as necessary to form a primer layer, and a thermoplastic resin is applied on the primer layer. It can be manufactured by forming an adhesive layer.

B. Laminated film FIG. 4 is a schematic cross-sectional view showing an example of a laminate film that is another embodiment of the laminated film of the present disclosure, in which the base layer 1 in the transfer film 10 illustrated in FIG. 2 is composed of three primer layers and an adhesive layer. It is the same as in FIG. 2 except that it is located between 4 and 4. That is, the laminated film 10 of this embodiment shown in FIG. 4 includes a hard coat layer 2, which is a cured product layer of the curable resin composition of the present disclosure, a primer layer 3, a base material layer 1, and an adhesive layer 4 in this order. We are prepared. Moreover, when providing a decoration layer, it is possible to provide it between a base material layer and a primer layer.

By having an adhesive function on the outermost surface opposite to the hard coat layer side, the laminated film of this embodiment can be used as a laminated film for lamination, and can be laminated to an adherend. For example, as illustrated in FIG. 4, the laminated film 10 of the present disclosure has an adhesive layer or an adhesive layer containing an adhesive or a pressure-sensitive adhesive on the surface opposite to the surface on the hard coat layer 2 side. ) 4, the laminated film of this embodiment can be laminated and attached to an adherend via an adhesive layer. Moreover, the laminated film 10 of this embodiment may be in a mode in which the base layer 1 has an adhesion function to an adherend, so that it can be laminated to an adherend without providing an adhesive layer.

FIG. 5 is a schematic cross-sectional view showing an example of a laminate obtained by laminating the laminate film shown in FIG. 4 to a resin substrate. The laminate 20 illustrated in FIG. 5 includes a resin base 21, an adhesive layer 4, a base layer 1, a primer layer 3, and a hard coat layer 2 in this order. Moreover, when providing a decoration layer, it is possible to provide it between a base material layer and a primer layer.

By laminating the laminate film of this embodiment on a resin substrate to obtain a laminate, the hard coat layer is located as the outermost layer, so the abrasion resistance, processability (extensibility), and chemical resistance of the laminate are improved. can be improved.

Each structure of the laminate film of this embodiment will be explained below. Note that the details of the hard coat layer, primer layer, and decorative layer in the laminate film of this embodiment are the same as those explained in the section "A. Transfer film" above, so the explanations here will be omitted. .

1. Base Material Layer The base material layer in the laminate film of this embodiment is arranged between the primer layer and the adhesive layer. In the laminate film of this embodiment, the base material layer is not peeled off when the laminate film of this embodiment is laminated to the resin substrate, and the other components are placed on the resin substrate.

The base material layer is not particularly limited, and for example, resin films such as acrylic resin film, polyester resin film, polyolefin resin film, and polyvinyl chloride resin film can be used.

The transparency of the base layer does not matter. Further, the base layer may be a colored base layer containing a colorant, or may be colorless.

In this aspect, at least the surface of the base layer on the hard coat layer side may be subjected to a known surface modification treatment, or may be provided with a coating layer of an easily adhesive coating agent. This is because the adhesion between the base layer and the hard coat layer can be improved.

The thickness of the base material layer is not particularly limited, but may be, for example, 4 μm or more and 200 μm or less. The base material layer may have a single layer structure or a multilayer structure. In the case of a multilayer structure, the thickness of the entire multilayer structure can be within the above range.

2. Adhesive Layer The laminate film of this embodiment can have an adhesive layer on the surface of the base layer opposite to the surface on the primer layer side. This is because the hard coat film of this embodiment can be laminated and attached to the resin substrate via the adhesive layer.

In this aspect, the adhesive layer can be an adhesive layer containing an adhesive (adhesive layer) or an adhesive layer containing an adhesive (adhesive layer). The resin constituting the adhesive layer or the pressure-sensitive adhesive layer is not particularly limited, and may be the same as the resin contained in general adhesives or pressure-sensitive adhesives used for laminating purposes. For example, acrylic resin, ester resin, urethane resin, ethylene vinyl acetate resin, latex resin, epoxy resin, polyurethane ester resin, vinylidene fluoride resin (PVDF), vinyl fluoride resin (PVF), etc. Examples include fluororesins, polyimide resins such as polyimide, polyamideimide, and polyetherimide, and rubber.

Further, in this aspect, the adhesive layer may be a heat seal layer. The heat seal layer is the same as that explained in the section "4. Adhesive layer" in "A. Transfer film" above, so the explanation here will be omitted.

The thickness of the adhesive layer is not particularly limited, but can be appropriately set so as to provide sufficient adhesive strength when attaching the laminate film of this embodiment to a resin substrate. For example, it can be 1 μm or more and 7 μm or less, preferably 1 μm or more and 6 μm or less.

In the laminate film of this embodiment, the base layer and the adhesive layer are formed separately, but the base layer and the adhesive layer may be integrally formed. A single layer formed integrally with the base material layer and an adhesive layer on the surface of the base material layer opposite to the surface on the decorative layer side can be used as a base material layer and an adhesive layer. The base material layer/adhesive layer can exhibit both a function as a base material layer and an adhesive function, for example, when the base material layer contains a thermoplastic resin.

3. Manufacturing method The method for manufacturing the laminate film of this embodiment is not particularly limited, but for example, a primer composition is applied on one side of the base layer and cured as necessary to form a primer layer. A hard coat layer-forming composition is applied and cured on top to form a hard coat layer, and an adhesive or pressure-sensitive adhesive is applied to the surface of the base layer opposite to the primer layer side for bonding. It can be obtained by forming a layer.

IV. Laminate The present disclosure provides a laminate having a resin base and a hard coat layer laminated on the resin base, wherein a primer layer and an adhesive layer are provided between the resin base and the hard coat layer. The above-mentioned hard coat layer provides a laminate which is a cured product of the above-mentioned curable resin composition. The laminate of the present disclosure is roughly divided into two aspects depending on the layer configuration. Hereinafter, each embodiment of the laminate will be explained.

A. Laminate using transfer film The laminate of this embodiment is a laminate manufactured using the above-mentioned transfer film. FIG. 3, which has already been described, is a schematic cross-sectional view showing an example of the laminate of this embodiment. This laminate 20 has a resin base 21, an adhesive layer 4, a primer layer 3, and a hard coat layer 2 in this order, and the hard coat layer is a cured product of the above-mentioned curable resin composition. Further, as detailed in the section "A. Transfer film" of "III. Laminated film" above, a decorative layer may be further provided.
According to the laminate of this embodiment, since the hard coat layer is located as the outermost layer, the abrasion resistance, processability (extensibility), and chemical resistance of the laminate can be improved.

Each structure of the laminate of this embodiment will be explained below. Note that the adhesive layer, primer layer, decorative layer, hard coat layer, etc. in the laminate of this embodiment have been explained in detail in the section "A. Transfer film" of "III. Laminated film" above, so they will not be described here. Explanation will be omitted.

1. Resin substrate There are no particular restrictions on the resin substrate used as the adherend, but examples include exterior and interior materials for architectural structures in general residences and public facilities, interior and exterior parts for automobiles, solar cell covers, solar cell substrates, and home appliances. Examples include members, illumination covers, front plates or covers of various display devices, lenses used in traffic lights and optical equipment, and the like. In the transfer sheet of the present disclosure, the resin substrate may be any resin molded product that is required to have hard coat properties (scratch resistance, etc.), but is preferably transparent and strong, and can be used as a substitute for current glass. Examples include organic glass. Specific examples of the organic glass include polycarbonate, polymethyl methacrylate, polyacrylate, polyethylene terephthalate, polyethylene naphthalate, polyolefin, ABS, and the like. Among these organic glasses, polycarbonate is preferably used because it has excellent impact resistance and transparency.

B. Laminate using laminate film The laminate of this embodiment is a laminate manufactured using the above-mentioned laminate film. FIG. 5, which has already been described, is a schematic cross-sectional view showing an example of the laminate of this embodiment. This laminate 20 has a resin base 21, an adhesive layer 4, a base layer 1, a primer layer 3, and a hard coat layer 2 in this order, and the hard coat layer is made of the above-mentioned curable resin composition. It is a cured product.

According to the laminate of this embodiment, since the hard coat layer is located as the outermost layer, the abrasion resistance, processability (extensibility), and chemical resistance of the laminate can be improved.

Each structure of the laminate of this embodiment will be explained below. In addition, regarding the resin substrate, adhesive layer, primer layer, decorative layer, hard coat layer, etc. in the laminate of this embodiment, "A. Transfer film" and "B. Laminate film" of the above "III. Laminated film", Since it was explained in detail in the section of "A. Laminate using transfer film" of "IV. Laminate", the explanation here will be omitted.

C. Manufacturing method The method for manufacturing the laminate of the present disclosure may be, for example, a step of arranging a laminate film on the surface of a resin base prepared in advance. Further, the step may be such that the formation of the resin substrate and the arrangement of the laminated film are performed simultaneously. Hereinafter, the former process will be referred to as a first manufacturing process, and the latter process will be referred to as a second manufacturing process.

1. First manufacturing process As a method for manufacturing a laminate according to the first manufacturing process described above, a resin substrate is molded by extrusion molding or the like, and immediately after or after cooling, the adhesive layer of the laminated film of the present disclosure is formed using a roll or the like. An example of this method is to press the surface of the resin substrate onto the resin substrate and laminate the resin substrate. When pressing the surface of the adhesive layer of the laminated film of the present disclosure onto the resin substrate, the adhesive layer may be heated to such an extent that at least a portion thereof is melted, if necessary. The laminated film can be heated by preheating the transfer film before pressure bonding, heating simultaneously with pressure bonding using a hot pressure roll, or the like. Further, the resin substrate may be preheated before the transfer.

When the laminated film of the present disclosure is a transfer film, the transfer base material layer for transfer may be peeled off and removed after the transfer film of the present disclosure is attached to a resin substrate. Furthermore, after the transfer film of the present disclosure is attached to the resin substrate, it may be further subjected to a molding process such as bending. Such a molding process may be performed either before or after peeling off the transfer base material layer.
In the laminated film of the present disclosure, since the cured material layer has excellent workability (extensibility), cracks are unlikely to occur even when such bending is performed.

2. Second Manufacturing Process In the second manufacturing process, the formation of the laminate and the arrangement of the laminate film are performed simultaneously. The resin substrate in the first manufacturing step is usually a molded body of solid resin. In this case, specific methods for producing the laminate include various injection molding methods such as insert molding, simultaneous injection molding decoration, blow molding, and gas injection molding.
That is, the second manufacturing step may be a step in which the steps of forming a resin substrate using an injection molding method and arranging the laminated film on the surface of the resin substrate are performed simultaneously.
In the present disclosure, it is particularly preferable to use an insert molding method or an injection molding simultaneous decoration method.

(i) Insert molding method A case will be described in which the second decorating step in the present disclosure is a step using an insert molding method.
Here, the insert molding method is a method in which a laminated film is placed on the surface of a resin substrate, and the resin substrate and the laminated film are placed simultaneously. In the insert forming method, the laminated film is formed into the shape of the surface of the article in advance, and the molded laminated film is placed in an injection mold, the injection mold is closed, and the resin composition in a fluid state is poured into the mold. It has at least an injection step of injecting the resin into the injection mold, and a solidification step of solidifying the injected resin composition to form a resin base and disposing a laminated film on the surface of the resin base.

When the laminated film of the present disclosure is used in an insert molding method, the configuration of the laminated film is preferably in the form of the laminated film described above.

(ii) Simultaneous injection molding decoration method A case will be described in which the second decorating step in the present disclosure is a step using a simultaneous injection molding decoration method.
Here, the injection molding simultaneous decoration method is a method in which a laminated film is placed on the surface of a resin substrate, and is a method in which molding of the resin substrate and placement of the laminated film are performed simultaneously. The injection molding simultaneous decoration method is also called an in-mold molding method. In the injection molding simultaneous decoration method, for example, a preforming process of preforming a laminated film using a dual-purpose female mold having the functions of a female mold and a vacuum molding mold, and a preforming process of preforming the laminated film The injection mold in which is placed is closed, and the resin composition in a fluid state is injected into the injection mold, and the injected resin composition is solidified to mold the article. and a solidification step of arranging a laminated film on the surface.

In the injection molding simultaneous decoration method, the laminate film explained in "III. Laminated film B. Laminated film" above may be used, or the transfer film explained in "III. Laminated film A. Transfer film" may be used. is also good, but the latter is more preferable. This is because the decorated article can be easily removed from the injection mold after the solidification step.

Note that the present disclosure is not limited to the above embodiments. The above-mentioned embodiments are illustrative, and any embodiment that has substantially the same configuration as the technical idea stated in the claims of the present disclosure and provides similar effects is the present invention. within the technical scope of the disclosure.

Hereinafter, the present disclosure will be specifically described by showing examples. These descriptions do not limit the present disclosure.

(Examples 1 to 8, Comparative Examples 1 to 5)
(1) Preparation of curable resin composition A curable resin composition was prepared having the ingredients and proportions (parts by mass) shown in Table 1 below. The urethane compound (A), acrylate compound (B), inorganic particles (C), and solvent used are as follows.

・Urethane compound 1 ^* : HDI nurate body - (PETA) 3
* Mixture with IPDI-(PETA)2 (HDI nurate form-(PETA)3: reaction product of pentaerythritol triacrylate and isocyanate having an isocyanurate ring derived from hexamethylene diisocyanate, IPDI-(PETA)2: Reaction product of pentaerythritol triacrylate and isophorone diisocyanate)
・Urethane compound 2: HDI nurate form-(HPA) 3
HDI nurate - (HPA) 3: Reaction product of isocyanate having an isocyanurate ring derived from hexamethylene diisocyanate and HPA (2-hydroxypropyl acrylate) - Acrylate compound 1: NK ester represented by the following formula A9300- 1CL (manufactured by Shin Nakamura Chemical Industry)

・Acrylate compound 2: NK ester A9300 (tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin Nakamura Chemical Industry) represented by the following formula)

・Acrylate compound 3: NK ester A9300-3CL represented by the following formula (manufactured by Shin Nakamura Chemical Industry)

・Comparative acrylate compound 4: PETA represented by the following formula

・Comparative acrylate compound 5: 1,6-hexanediol diacrylate (NK ester A-HDN) represented by the following formula

・Comparative acrylate compound 6: Neopentyl glycol diacrylate (light acrylate NP-A) represented by the following formula

・Inorganic particles 1: Silica ELCON V8803-25 (manufactured by JGC Catalysts & Chemicals) Solid content 40%, maximum particle size 25 nm, solvent MIBK (methyl isobutyl ketone), reactive irregularly shaped silica, silica particles with an average primary particle size of 10 nm to 100 nm The reactive group is a group containing an ethylenically unsaturated bond.Inorganic particle 2: Silica ELCON V8802 (manufactured by JGC Catalysts & Chemicals), solid content 40%, average primary particle size 12 nm, solvent MIBK (methyl isobutyl ketone), spherical silica, solvent: MEK (methyl ethyl ketone)

(2) Evaluation of elongation Each curable resin composition was coated on a PET film with a thickness of 75 μm that had been subjected to a release treatment at a coating weight of 5 ± 1 g/m ² using a bar coater #10, and then heated at 90°C. It was dried for 1 minute to form a coating film. The coating film was irradiated with an electron beam of 8 Mrd to obtain a laminated film having a cured layer of the curable resin composition on the surface.

The laminated film obtained in each example was cut into a size of 2.5 cm x 10 cm, and the sample was tested using a tensile tester (AUTOGRAPH AG-X manufactured by Shimadzu Corporation) at a distance between chucks of 5 cm and a tensile speed of 50 mm/min. A tensile test was conducted by pulling the entire PET film. The length of elongation when cracks appeared in the cured material layer was measured, and the elongation was determined and evaluated as described below.
Elongation = (length of elongation when cracks occur in the cured material layer) / (length of cured material layer before test) x 100 (%)

<Evaluation criteria>
○: 30% or more
△: 20% or more and less than 30% ×: less than 20%

(3) Abrasion resistance evaluation Each curable resin composition was coated on a PET film with a thickness of 50 μm that had been subjected to a release treatment at a coating amount of 5 ± 1 g/m ² using a bar coater #10, and then It was dried for 1 minute at ℃ to form a coating film. The coating film was irradiated with an electron beam of 8 Mrd to obtain a cured layer of the curable resin composition.

The following resin composition for forming a primer layer was applied to the above cured product layer using a bar coater #20 in a coating amount of 7±1 g/m ² , and then dried at 90° C. for 1 minute to obtain a primer layer.
(Resin composition for forming primer layer)
Polycarbonate urethane acrylic copolymer: 100 parts by mass Benzotriazole UV absorber: 17 parts by mass Hydroxyphenyltriazine UV absorber: 13 parts by mass Light stabilizer: 8 parts by mass Particles (silica particles, average particle size: 3 μm) : 9 parts by mass Curing agent (hexane methylene diisocyanate): 25 parts by mass Furthermore, after applying a heat-fusion resin (acrylic resin) to the above primer layer with a bar coater #20 at a coating amount of 7 ± 1 g/m ² , and dried at 90° C. for 1 minute to form a laminated film. The laminated film was bonded to a polycarbonate (PC) plate measuring 10 cm x 10 cm and 2 mm thick using a hot laminating roll. Thereafter, the PET film of the PC transfer plate was peeled off to obtain a laminate.

The laminate obtained in each example was cut into a size of 10 cm x 10 cm, and the sample was subjected to a Taber abrasion test according to JIS K7105 using a wear ring CS-10F, a load of 500 g, and a rotation speed of 500 revolutions. The difference in haze value ΔH% was measured.

<Evaluation criteria>
○: ΔH% is less than 3.0% △: ΔH% is 3.0% or more and less than 5.5% ×: ΔH% is 5.5% or more

(4) Ethanol resistance evaluation 8 to 10 drops of neoethanol were dropped with a dropper onto a 1 cm square piece of Ben cotton on the surface of the hard coat layer of the laminate produced in the same manner as in the above abrasion resistance evaluation to prevent the solvent from volatilizing. It was covered with a cover and left for 24 hours.
○: No change △: Slight cracking ×: Large cracking

The above evaluation results are also shown in Table 1.

With the curable resin composition of the present disclosure, a cured product having excellent abrasion resistance, elongation properties, and chemical resistance could be obtained.

1... Base material layer 2... Resin cured material layer (hard coat layer)
3...Primer layer 4...Adhesive layer 10...Laminated film 20...Laminated body 21...Resin base

Claims (7)

(A) a urethane compound that is a reaction product of a compound (a1) represented by the following general formula (1) and an isocyanate ring-containing isocyanate ring (a2) represented by the following general formula (2);
(B) a compound having an isocyanurate ring represented by the following general formula (3);
(C) A curable resin composition comprising inorganic particles having an average primary particle size of 10 nm to 100 nm.
(In the formula, Z ¹ is a (meth)acryloyloxy group . ^{R 1} is a methylene group . ^{R 2} is a hydrogen atom or a monovalent hydrocarbon group. R ³ is a methylene group . .n is an integer from 1 to 3, m is an integer from 1 to 3, and n+m is a number satisfying 3 to 4. When n is 2 or more, two or more Z ¹ and R ¹ are the same. may be the same or different. When m is 2 or more, two or more ^R3s may be the same or different . )
(In the formula, each R ⁴ is independently a linear, branched, or cyclic divalent aliphatic hydrocarbon group .)
(In the formula, Z ² is each independently a (meth)acryloyloxy group . R ⁵ is each independently the same or different divalent hydrocarbon group which may contain an oxygen atom , and three At least one of R ⁵ is a divalent aliphatic hydrocarbon group having 5 to 15 carbon atoms and containing an ester group .) (A) a urethane compound that is a reaction product of a compound (a1) represented by the following general formula (1) and an isocyanate ring-containing isocyanate ring (a2) represented by the following general formula (2);
(B) a compound having an isocyanurate ring represented by the following general formula (3);
(C) Inorganic particles with an average primary particle size of 10 nm to 100 nm
including
Furthermore, a curable resin composition containing a reaction product of the compound represented by the above general formula (1) and an isocyanate that does not contain an isocyanurate structure and has an alicyclic structure.
(In the formula, Z ¹ is a polymerizable carbon-carbon double bond-containing group. R ¹ is a divalent hydrocarbon group which may contain an oxygen atom. R ² is a hydrogen atom or a monovalent hydrocarbon group. R ³ is a single bond or a divalent hydrocarbon group. n is an integer from 1 to 3, m is an integer from 1 to 3, and n+m is a number satisfying 2 to 4. When n is 2 or more, two or more Z ¹ and R ¹ may be the same or different. When m is 2 or more, 2 or more R ³ may be the same or different. When 4-n-m is 2, two R ² may be the same or different. )
(In the formula, R ⁴ are each independently the same or different divalent hydrocarbon groups which may contain an oxygen atom. )
(In the formula, Z ² are each independently a (meth)acryloyloxy group. R ⁵ are each independently the same or different divalent hydrocarbon groups which may contain an oxygen atom, and three R ⁵ At least one of them is a divalent aliphatic hydrocarbon group having 5 to 15 carbon atoms and containing an ester group. ) The curable resin composition according to claim 1 , further comprising a reaction product of the compound represented by the general formula (1) and an isocyanate that does not contain an isocyanurate structure and has an alicyclic structure. A cured resin product, which is a cured product of the curable resin composition according to any one of claims 1 to 3 . A laminated film having a cured resin layer, which is a layer of the cured resin according to claim 4 , on a base layer. A transfer film comprising a transfer base material layer and a hard coat layer laminated on the transfer base material layer,
A transfer film, wherein the hard coat layer is a cured product of the curable resin composition according to any one of claims 1 to 3 . A laminate comprising a resin base and a hard coat layer laminated on the resin base,
having either one or both of a primer layer and an adhesive layer between the resin base and the hard coat layer,
A laminate, wherein the hard coat layer is a cured product of the curable resin composition according to any one of claims 1 to 3 .