JP2022144276A - Curable resin composition and laminated film using the same - Google Patents

Abstract

To provide a curable resin composition which enables formation of a film having both stretchability and scratch resistance.SOLUTION: A curable resin composition contains a urethane urea compound having a radical-polymerizable group, and a branched alkylene group having 6 to 10 carbon atoms.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a novel curable resin composition and a laminated film using the same.

BACKGROUND ART Surface coating technology is applied to the interior or exterior of industrial products such as automobiles and home electric appliances in order to improve their abrasion resistance (scratch resistance), design and the like. Conventionally, a method of separately forming a surface coat layer on a molded product that has been molded in advance by injection molding or the like has been adopted. In this case, the method of forming the surface coat layer includes, in addition to the coating method, a water pressure transfer method in which a pre-printed water-soluble film is spread on the surface of water to transfer the printed layer to the product.

As a coating agent, various resin compositions are known. In recent years, a coating agent using a polyurethane urea resin has been proposed because a hard coat layer having excellent scratch resistance and the like can be formed.

For example, a polyurethane urea resin composition obtained from a polyol (A), a polyisocyanate (B), a diamine (C), and a monoamine (M), wherein the polyol (A) is a polycarbonate diol having a number average molecular weight of 2,200 to 6,000. (a1), the polyisocyanate (B) contains an alicyclic diisocyanate (b1), and the polyurethane urea resin composition has a number average molecular weight of 30,000 to 90,000 ( Patent document 1)

Further, for example, a polyurethane urea resin (U) and a solvent (S ), wherein the weight ratio of ethylene, which is a constituent monomer of the hydroxyl group-modified polyolefin (A), to an α-olefin having 3 to 8 carbon atoms (ethylene:α-olefin) is 5 : 95 to 95:5, the isotacticity of the α-olefin unit chain portion of the hydroxyl group-modified polyolefin (A) is 1 to 50%, and the number average molecular weight of the hydroxyl group-modified polyolefin (A) is 1,000. ∼6,000 is known (Patent Document 2).

In recent years, insert molding or the like is becoming mainstream, in which a cured film (precure type) prepared in advance is used as a hard coating material and this is integrally molded with a separately prepared resin composition. For example, as shown in FIG. 1, after placing a laminated film 10 in which a cured film 12 (hard coat) is laminated on a base film 11 as a mold between a male mold 21a and a female mold 21b (see FIG. 1 ( a)), the molten resin 13a is poured into a mold for injection molding (FIG. 1(b)). After the resin is cured, the unnecessary portion of the base film 11 is cut (trimmed), and the molding 30 (product) composed of the resin layer 13/base film 11/cured film 12 is removed from the mold (FIG. 1(c)). )). In this way, it is possible to provide a molded article having a hard coat of a cured film on the outermost surface.

JP 2019-157055 JP 2021-21059

Since the pre-cure type film is further subjected to thermoforming (insert molding, etc.) after the cured film is produced as described above, it may have stretchability (moldability) sufficient to withstand the thermoforming. is necessary. That is, even if the surface is subjected to processing such as bending, it is required to have properties that can follow the processing without causing cracks or the like on the surface. For example, as shown in part A of FIG. 1B, particularly when the molded body 30 has a portion that bends in its thickness direction, the functional layer 12 needs to follow the base film 11 at that portion. be. If it cannot be followed, problems such as peeling of the functional layer 12 from the base film 11 over time and cracking of the functional layer 12 occur. Therefore, the functional layer 12 is required to have excellent adhesion to the base film and to have high stretchability and the like.

However, in general, when an attempt is made to increase the stretchability of the film, the hardness of the film decreases, and the desired scratch resistance cannot be obtained. On the other hand, if the scratch resistance is improved, the stretchability is lowered, making it difficult to use as a pre-cure type film. Thus, in the pre-cure type film, although there is a demand for a film that has both stretchability and scratch resistance, such a film is still being developed because the physical properties of the two contradict each other. It is the current situation that it has not reached.

Accordingly, the main object of the present invention is to provide a curable resin composition capable of forming a film having both stretchability and scratch resistance.

As a result of intensive research in view of the problems of the prior art, the inventors of the present invention have found that the above objects can be achieved by adopting a composition having a specific composition, and have completed the present invention.

That is, the present invention relates to the following curable resin composition and a laminated film using the same.
1. A curable resin composition containing a urethane urea compound having a radically polymerizable group and a branched alkylene group having 6 to 10 carbon atoms.
2. Item 2. The curable resin composition according to Item 1, wherein part or all of the urethane urea compound further has a divalent aliphatic cyclic group which may be substituted with an alkyl group.
3. 3. The curable resin composition according to item 1 or 2, further comprising a (meth)acrylate compound and a photopolymerization initiator.
4. 4. The curable resin composition according to any one of Items 1 to 3, further comprising an organic solvent.
5. The urethane urea compound has the following properties:
In a cured urethane urea film having a thickness of 3 μm or more produced by irradiating a urethane urea compound with ultraviolet rays having a wavelength of 250 nm to 350 nm at an integrated light amount of 500 mJ/cm ² ,
(1) The elastic modulus when the Berkovich indenter is pushed by 1/10 of the thickness at a speed of 0.08 μm / sec is 3.5 GPa to 5.4 GPa, and (2) the Berkovich indenter is 0.08 μm. There is no inflection point in the "contact stiffness-displacement graph" when pushing at a speed of / sec until the load reaches 100 mN,
5. The curable resin composition according to any one of items 1 to 4, characterized by having
6. A laminated film obtained by laminating a cured film of the curable resin composition according to any one of items 1 to 5 on a substrate.
7. 7. The laminated film according to item 6, which is used for molding.
8. A molded article having the cured film of the laminated film according to item 6 or 7 on the outermost surface.
9. A method for producing a urethane urea compound, comprising:
(a) a polyisocyanate compound (b) a diol compound having 6 to 10 carbon atoms and having at least one of a secondary hydroxyl group and a tertiary hydroxyl group (c) a primary alkanolamine and/or a secondary alkanolamine (d) A method for producing a urethane urea compound, comprising the step of reacting a starting material containing a hydroxyl group-containing (meth)acrylate compound.
10. A urethane urea compound having the following properties:
In a cured urethane urea film having a thickness of 3 μm or more produced by irradiating a urethane urea compound with ultraviolet rays having a wavelength of 250 nm to 350 nm at an integrated light amount of 500 mJ/cm ² ,
(1) The elastic modulus when the Berkovich indenter is pushed by 1/10 of the thickness at a speed of 0.08 μm / sec is 3.5 GPa to 5.4 GPa, and (2) the Berkovich indenter is 0.08 μm. There is no inflection point in the "contact stiffness-displacement graph" when pushing at a speed of / sec until the load reaches 100 mN,
A urethane urea compound characterized by having

According to the present invention, it is possible to provide a curable resin composition capable of forming a film having both stretchability and scratch resistance. A cured film obtained from such a constituent resin composition can express a unique physical property having both hardness and softness, so to speak.

That is, since the urethane urea compound of the present invention has a structure in which a specific branched alkylene group and a radically polymerizable group are bonded in the urethane urea structure, it exhibits desired stretchability even after curing. can be subjected to the molding process without In addition, the cured film after molding exhibits high scratch resistance and can exhibit excellent performance as a hard coat.

An example of a process for manufacturing a laminate (molded body) by insert molding is shown. 4 is a graph (contact stiffness-displacement graph) showing the relationship between contact stiffness/indentation depth in each cured film of Example 1 and Comparative Example 2. FIG. FIG. 2 is a diagram showing the results of observing the appearance of a pressed portion in each cured film of Example 1 and Comparative Example 2. FIG.

10 laminated film 11 base film 12 cured film (cured film)
13a Molten resin 13 Resin layer after curing 21a Male mold 21b Female mold 30 Molded body (product)
A bent part

1. Curable resin composition (1) Urethane urea compound and its production method (1-1) Urethane urea compound The curable resin composition of the present invention (the composition of the present invention) comprises a radically polymerizable group and 6 to 10 carbon atoms. (hereinafter also simply referred to as "branched alkylene group").

In the present invention, hereinafter, an acryloyl group or a methacryloyl group is collectively referred to as a "(meth)acryloyl group" unless otherwise specified. An acryloyloxy group or a methacryloyloxy group is collectively referred to as a "(meth)acryloyloxy group". Furthermore, acrylate or methacrylate is generically called "(meth)acrylate", and acrylic acid or methacrylic acid is generically called "(meth)acrylic acid".

The compound of the present invention is a compound containing a urethane bond (--NHCOO--) and a urea bond (--NHCONH-- or --NHCON<). The urethane bond and the urea bond may each independently have one or two or more.

In addition, the urethane bond (hereinafter sometimes referred to as "A") and the urea bond (hereinafter sometimes referred to as "B") are, for example, a) alternately bonded via the organic group R If b) multiple of the same bonds form a segment through the organic group R, and the segments (i.e., the polyurethane structure and the polyurea structure) are linked together, c) both bonds randomly connect the organic group R or d) a combination of a) to c). The present invention includes any urethane urea structure composed of a) to d) above.

In particular, in the case of a) above, for example -R ¹ -AR ² -B-
as a repeating unit, and a structure in which one or more of these are combined.

In particular, in the case of b) above, for example, -R ¹ -AR ² -AR ³ -AR ⁴ -BR ⁵ -B-
-R ¹ -AR ² -AR ³ -BR ⁴ -BR ⁵ -B-
-R ¹ -AR ² -AR ³ -AR ⁴ -BR ⁵ -B-
-R ¹ -AR ² -AR ³ -AR ⁴ -BR ⁵ -BR ₆ -B-
-R ¹ -AR ² -AR ³ -AR ⁴ -BR ₅ -BR ₆ -BR ₇ -B-
is used as a repeating unit, and one or more of these are bonded (R ¹ to R ⁷ above are organic groups which may be different from each other).

At least one of the organic groups R bonded to the urethane bond or the urea bond should contain a radically polymerizable group and at least one should contain a branched alkylene group. Therefore, the organic group R itself may be a radically polymerizable group or a branched alkylene group.

Examples of the radically polymerizable group include, but are not limited to, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acrylamide group, a vinyl group, and an allyl group. These can also be used 1 type or in combination of 2 or more types.

Although the number of radically polymerizable groups per molecule of the compound of the present invention is not limited, it is usually about 2 to 10, preferably 6 to 10. Thereby, better curability can be exhibited.

The radically polymerizable group may be bonded to the terminal of the urethane urea structure, but may be bonded to a location other than the terminal. The terminal of the urethane urea structure may be an unreacted group such as an isocyanate group as long as it does not interfere with the effects of the present invention.

The branched alkylene group has 6 to 10 carbon atoms. If the number of carbon atoms is 5 or less, it becomes difficult to dissolve in general-purpose solvents such as methyl ethyl ketone (MEK). Moreover, when the number of carbon atoms is 11 or more, the scratch resistance becomes low. Also, the number of carbon atoms in the carbon chain of only the branched portion is preferably 4 to 8 in general. Furthermore, a branched alkylene group having one branch is particularly preferred.

Accordingly, specific examples of preferred branched alkylene groups include the following. These can also be used 1 type or in combination of 2 or more types.
_-CH2CH ( _{C4H9 )} -
_-CH2CH ( _{C5H11 )} -
_{-CH2CH ( C6H13} )-
_{-CH2CH ( C7H15} )-
_{-CH2CH ( C8H17} )-

Although the number of branched alkylene groups per molecule of the compound of the present invention is not limited, it is usually about 4 to 23, preferably 7 to 18. As a result, the solubility and the like of the compound of the present invention in general-purpose solvents (such as MEK) can be further enhanced.

The organic group R other than the radically polymerizable group and the branched alkylene group is not particularly limited, and for example, a cycloalkylene group, -NH-alkylene group, -O-alkylene group, -NH-cycloalkylene group, -O-cycloalkylene group, phenylene group, biphenylene group, —O-phenylene group, —O-biphenylene group and the like, as well as linear alkylene groups not bonded to the branched alkylene groups. These may be one or a combination of two or more.

These organic groups R may or may not have a substituent. Examples of substituents include the radically polymerizable groups and branched alkylene groups described above, as well as alkyl groups and the like. Therefore, in the present invention, for example, the organic group R may be a divalent aliphatic cyclic group which may be substituted with an alkyl group.

Although the number of carbon atoms in these organic groups R is not particularly limited, it is usually preferably about 2 to 15. When the organic group R has a substituent, the value also includes the carbon number of the substituent.

が挙げられる。 Specific examples of the organic group R include an organic group derived from the polyisocyanate compound used as the starting material. For example, the following organic groups R _a derived from dicyclohexylmethane 4,4′-diisocyanate:

is mentioned.

が挙げられる。これらは、１種又は２種以上を組み合わせて使用することもできる。 Also, the following organic group R _b derived from isophorone diisocyanate:

is mentioned. These can also be used 1 type or in combination of 2 or more types.

Although the molecular weight of the compound of the present invention is not particularly limited, the number average molecular weight is preferably about 3,000 to 10,000, more preferably 5,000 to 8,000, in terms of stretchability. Accordingly, the compounds of the present invention may be in the form of oligomers or polymers. The compounds of the present invention may have an acrylic equivalent of about 1000 to 1500 g/eq, a urethane equivalent of about 200 to 400 g/eq, and a urea equivalent of about 1000 to 2000 g/eq, but are not limited thereto.

The compounds of the invention exhibit the following properties:
In a cured urethane urea film having a thickness of 3 μm or more produced by irradiating a urethane urea compound with ultraviolet rays having a wavelength of 250 nm to 350 nm at an integrated light amount of 500 mJ/cm ² ,
(1) The elastic modulus is 3.5 GPa to 5.4 GPa when the Berkovich indenter is pushed by 1/10 of the thickness at a speed of 0.08 μm / sec (characteristic A), and (2) Berkovich indenter There is no bending point in the "contact stiffness-displacement graph" when the is pushed at a speed of 0.08 μm / sec to a load of 100 mN (characteristic B),
It is desirable to have

The above physical properties A and B are physical properties related to the stretchability (or moldability) of the cured film of the compound of the present invention, and are indicators of the ability of the compound of the present invention to form a cured film with excellent stretchability. be. Mainly, the physical property A is an index of hardness of the cured film, and the physical property B is an index of brittleness. The cured film to be evaluated contains the compound of the present invention. It is a physical property based on the liquid composition.

Characteristic A also indicates ease of molding (or difficulty of molding), and good moldability can be maintained within the above numerical range.

Characteristic B indicates that when the specific indenter is pushed into the cured film, cracks do not occur in the part or its surroundings. The presence of bending points indicates that cracks have occurred around the indentation. The cured film of the compound of the present invention has the property of being resistant to cracking even when a local force is applied from the outside. Therefore, for example, even if a load such as bending is applied to the cured film during molding, it is possible to obtain a molded product in which cracks or the like are less likely to occur on the surface of the cured film.

Since the compound of the present invention satisfies both the above properties A and B, it exhibits a certain level of durability even when subjected to a specific stress from the outside. is suitable for

As such a compound of the present invention, a compound produced by "(1-2) Method for producing a urethane urea compound" described later can also be suitably employed. That is, a reaction product obtained by reacting at least components (a) to (d) described below can be suitably used as the compound of the present invention.

(1-2) Method for producing urethane urea compound Although the method for producing the compound of the present invention is not particularly limited, the following method can be suitably employed. That is, for example, (a) a polyisocyanate compound, (b) a diol compound having 6 to 10 carbon atoms and having at least one of a secondary hydroxyl group and a tertiary hydroxyl group, (c) a primary alkanolamine and/or The compound of the present invention can be suitably prepared by a method comprising reacting starting materials containing a secondary alkanolamine and (d) a hydroxyl group-containing (meth)acrylate compound.

(a) Polyisocyanate compound The polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule. Aromatic polyisocyanates such as, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate , lysine diisocyanate, lysine triisocyanate and other aliphatic polyisocyanates; In addition, isocyanate trimers or oligomers (adducts, burettes, isocyanurates, allophanates) can be used. These may be used individually by 1 type, and may be used in combination of 2 or more types. In the present invention, dicyclohexylmethane 4,4'-diisocyanate is particularly preferred.

(b) a diol compound having 6 to 10 carbon atoms and having at least one hydroxyl group of a secondary hydroxyl group and a tertiary hydroxyl group A diol compound having a carbon number of 6 to 10 in the entire diol compound, and at least one of the two hydroxyl groups possessed by the diol compound is a secondary hydroxyl group (a hydroxyl group bonded to a secondary carbon atom ) or a tertiary hydroxyl group (a hydroxyl group attached to a tertiary carbon atom).

（但し、Ｒ^８は、炭素数４～８の直鎖アルキル基を示す。）
で示されるジオール化合物を好適に用いることができる。 Examples of the diol compound having 6 to 10 carbon atoms and having at least one of a secondary hydroxyl group and a tertiary hydroxyl group include, but are not limited to, 1,2-hexanediol, 1,2-octanediol, 1,2-octanediol, 2-nonanediol, 1,2-decanediol, 3,3-dimethyl-1,2-butanediol, 2,3-dimethyl-2,3-butanediol, 2,3-dimethyl-1,2-butanediol , 2-methyl-2,4-pentanediol and the like. These can be used singly or in combination of two or more. In particular, according to the invention, the following formula:

(However, R ⁸ represents a linear alkyl group having 4 to 8 carbon atoms.)
A diol compound represented by can be preferably used.

The amount of the diol compound to be blended is not particularly limited, but it is usually preferably about 0.5 to 0.9 mol, particularly 0.6 to 0.8 mol, per 1 mol of the polyisocyanate compound. is more preferable.

(c) Primary alkanolamine and/or secondary alkanolamine The primary alkanolamine and/or secondary alkanolamine is a compound having a primary or secondary amino group and a hydroxyl group. is not particularly limited, such as monoethanolamine, diethanolamine, diisopropanolamine, 1,1,2,2-tetramethylmonoethanolamine, monoisopropanolamine, N-methylethanolamine, N-butylethanolamine, 2- amino-2-methyl-1-propanol, 2-methyl-2-aminomethyl-1-propanol and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types. In the present invention, monoethanolamine is particularly preferred.

Although the amount of the alkanolamine compounded is not particularly limited, it is usually preferably about 0.05 to 0.45 mol, particularly 0.15 to 0.35 mol, per 1 mol of the polyisocyanate compound. is more preferable.

The mixing molar ratio of the diol having a branched structure and the alkanolamine is not particularly limited, but it is usually preferably about 1.5:1 to 9:1. By setting the content within this range, better chemical resistance and better solvent solubility can be obtained.

(d) Hydroxyl Group-Containing (Meth)Acrylate Compound The hydroxyl group-containing (meth)acrylate compound is not particularly limited as long as it has one or more hydroxyl groups. For example, alkyl groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate hydroxyalkyl (meth)acrylate having 1 to 16 (preferably 1 to 12) carbon atoms; 2-hydroxyethyl (meth)acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone modification 2-Hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like ethylenically unsaturated group 1 compound having two ethylenically unsaturated groups such as glycerin di(meth)acrylate, 2-hydroxy-3-(meth)acryloyl-oxypropyl(meth)acrylate, pentaerythritol tri(meth)acrylate, caprolactone Modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate Compounds having 3 or more ethylenically unsaturated groups such as acrylates and succinic acid-modified pentaerythritol tri(meth)acrylates can be mentioned.

The amount of the acid group-containing (meth)acrylate compound is not particularly limited, but it is usually preferably about 0.02 to 0.2 mol, particularly 0.05 to 0.2 mol, per 1 mol of the polyisocyanate compound. More preferably 0.15 mol.

The reaction in the production method of the present invention is usually preferably a liquid phase reaction in an organic solvent. Examples of organic solvents include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, and methoxypropyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, dibutyl ether, tetrahydrofuran, and propylene glycol. Various organic solvents such as ether solvents such as monomethyl ether acetate and diethylene glycol dimethyl ether, and aromatic solvents such as toluene and xylene can be used. In particular, in the present invention, it is preferable to use a ketone-based solvent from the standpoint of adhesion and the like.

In the present invention, it is preferable to form a solution by dissolving each component in an organic solvent. A good coating film can be formed by coating by preparing a solution in which all the components are dissolved.

When an organic solvent is used, the amount of the organic solvent to be used is not limited. For example, the amount of the organic solvent may be appropriately set within the range of 10 to 90% by weight according to the type of components to be used, the desired viscosity, etc. .

In the production method of the present invention, each of these components may be dissolved in an organic solvent and then subjected to a predetermined reaction step.

Although the reaction conditions are not limited, the following conditions are preferred. First, as the order of reacting each component, (A) (a) a polyisocyanate compound and (b) a diol compound having at least one of a secondary hydroxyl group and a tertiary hydroxyl group and having 6 to 10 carbon atoms are reacted. (B) adding (c) a primary alkanolamine and/or a secondary alkanolamine to the resulting reaction solution for reaction; (C) adding (d) a hydroxyl group to the resulting reaction solution A method including a step of adding a (meth)acrylate compound and allowing it to react can be suitably employed. As a result, the urethane urea structure can be formed more reliably and a desired organic group (ie, a branched alkylene group and a radically polymerizable group) can be imparted to the urethane urea structure.

Although the reaction temperature is not particularly limited, it is usually about 20 to 110°C, preferably 60 to 90°C.

The finally obtained compound of the present invention can usually be obtained in a liquid form, and can be used as it is as the composition of the present invention. The composition of the present invention can also be prepared by further mixing other ingredients as necessary.

(2) Curable resin composition of the present invention The composition of the present invention contains the compound of the present invention as an essential component, and usually takes the form of a solution in which the compound of the present invention is dissolved in an organic solvent.

The composition of the present invention may optionally contain additives other than the compound of the present invention, but preferably further contains a (meth)acrylate compound and a photopolymerization initiator. Thereby, higher scratch resistance and the like can be obtained.

(Meth) acrylate compound The (meth) acrylate compound is not limited as long as it can contribute to curing, for example, an alkyl group-containing (meth) acrylate compound, an aromatic ring-containing (meth) acrylate compound, an ether chain-containing (meth) acrylate Various compounds such as compounds, nitrogen-containing (meth)acrylate compounds can be used. These (meth)acrylate compounds may be either compounds containing hydroxyl groups or compounds not containing hydroxyl groups. These can be used singly or in combination of two or more.

Examples of the alkyl group-containing (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, and tert-butyl (meth)acrylate. , isodecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate , linear or branched alkyl group-containing (meth)acrylic acid ester monomers such as isostearyl (meth)acrylate.

Examples of the aromatic ring-containing (meth)acrylate compounds include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethoxylated o-phenyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 2 -hydroxy-3-phenoxypropyl (meth)acrylate and the like.

Examples of the alicyclic structure-containing (meth)acrylate compound include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl methacrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)methyl ( meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, 1-adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylates and the like.

Examples of the ether chain-containing (meth)acrylate compounds include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-isopropoxyethyl methacrylate, 3-methoxybutyl (meth)acrylate, 2-butoxy Ethyl (meth) acrylate, 2-butoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, octoxypolyethyleneglycol-polypropyleneglycol-mono(meth)acrylate, lauroxypolyethyleneglycol mono(meth)acrylate, stearoxypolyethyleneglycol mono(meth)acrylate (Meth)acrylate and the like.

Examples of the nitrogen-containing (meth)acrylate compounds include t-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, pentamethylpiperidinyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (Meth)acrylate, acryloylmorpholine, dimethylaminoethyl methacrylate quaternary product, dimethylacrylamide, isopropylacrylamide and the like.

Examples of hydroxyl group-containing (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6- Hydroxyhexyl (meth)acrylate, pentaerythritol tri(meth)acrylate and the like. Other examples include monomers having multiple (meth)acryloyl groups such as pentaerythritol tetra(meth)acrylate.

Photopolymerization Initiator The photopolymerization initiator is not particularly limited as long as it initiates polymerization by active energy rays such as electron beams (EB), ultraviolet rays (UV), and infrared rays (IR). For example, dimethyl-2,2′-azobis(2-methylpropionate), 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylbenzophene, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, benzyldimethylketal, 1-hydroxycyclohexyl-phenylketone, benzoin methyl ether, benzoin Ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide , bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methylbenzoylformate, 2-benzyl-2-dimethyl amino-4-morpholinobutyrophenone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one and the like. These can be used alone or in combination of two or more. Known or commercially available photopolymerization initiators can also be used.

The content of the photopolymerization initiator can be appropriately set according to the type of photopolymerization initiator used, etc., but is usually about 1 to 10% by weight in 100% by weight of the composition of the present invention (solid content). It may be within the range, and from the viewpoint of curability, it is particularly preferably 1 to 5% by weight.

Furthermore, in the composition of the present invention, additives contained in known hard coats can be appropriately blended as optional components within a range that does not impair the effects of the present invention. For example, cross-linking agents, inorganic fine particles (silica, alumina, titania, zirconia and other oxide fine particles), antifouling agents (slip agents), surface control agents (silicone compounds, fluorine compounds), UV absorbers, light stabilizers , dispersants (surfactants), wetting agents, thickeners, antioxidants, polymerization inhibitors, polymerization modifiers, colorants and the like.

The curable composition of the present invention preferably dissolves each component in an organic solvent to form a solution. Examples of organic solvents include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, and methoxypropyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, dibutyl ether, tetrahydrofuran, and propylene glycol. Various organic solvents such as ether solvents such as monomethyl ether acetate, diethylene glycol dimethyl ether and propylene glycol monomethyl ether, and aromatic solvents such as toluene and xylene can be used. The amount of the organic solvent to be used is not limited, and can be appropriately adjusted, for example, within a range such that the solid content is 1 to 50% by weight.

The composition of the present invention can be prepared by uniformly mixing the above components. Moreover, the mixing order of each component is not limited, either. The temperature and the like at the time of mixing are not limited, and the mixing can be carried out, for example, at room temperature and normal pressure. Mixing can be carried out using known or commercially available devices such as mixers and kneaders.

2. Laminated Film The present invention includes a laminated film obtained by laminating a cured film of the composition of the present invention on a substrate. That is, the present invention includes a laminated film comprising a substrate and a cured film of the composition of the present invention formed thereon.

The laminated film may be transparent, translucent or opaque, but the laminated film of the present invention is preferably transparent. The haze value in the case of being transparent is not limited, but it is usually desirable to be about 0.1 to 5%.

Also, the cured film may be transparent, translucent or opaque, but the laminate film of the present invention is preferably transparent. Although the haze value when transparent is not limited, it is usually desirable to be about 0.1 to 5%.

The laminated film of the present invention may be laminated with other layers as necessary, as long as the cured film becomes the outermost surface during use. Examples thereof include various layers such as an antistatic layer, a moisture shielding layer, an adhesive layer, an anchor coat layer, a primer layer, a printing layer, and an antireflection layer.

The thickness of the laminated film can be appropriately set according to the type of substrate used, the application of the laminated film, and the like, and can be, for example, about 30 to 1000 μm, but is not limited to this.

Since the laminate film of the present invention is particularly excellent in the stretchability of the cured film, it can be suitably used as a material for producing a desired molded article by molding the cured film. Therefore, it is most suitable as a film used for molding. More specifically, although the cured film has excellent scratch resistance, it has high stretchability, so even if the laminated film containing the cured film is molded, it deforms into a desired shape. As a result, it is possible to produce a molded article substantially free from surface cracks and the like. As a result, it is possible to provide products having an excellent hard coat on the surface of various molded products.

The method for producing the laminated film of the present invention is not particularly limited. A laminate film can be preferably produced by a method including a step of forming a cured film by irradiation (curing step).

Coating Film Forming Step In the coating film forming step, a coating film of the composition of the present invention is formed on the substrate. Although the method for forming the coating film is not particularly limited, it can be formed, for example, by applying the liquid composition of the present invention onto a substrate. The coating method is not particularly limited, and for example, methods using brush coating, spraying, immersion, doctor blade, bar coater, etc., as well as printing methods such as screen printing, gravure printing and offset printing can be employed.

A drying process can also be implemented with respect to a coating film as needed. The drying method is not limited, and for example, drying by heating can be employed in addition to natural drying. The heating temperature may be within a range that does not adversely affect the base material, and can be, for example, about 70 to 120° C., but is not limited to this.

Films made of various materials such as synthetic resins, rubbers, and metals can be suitably used as the substrate. In particular, synthetic resins include polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyolefins (polyethylene, polypropylene, etc.), celluloses (cellophane, diacetylcellulose, triacetylcellulose, etc.), and polyvinyl chloride. , polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polyetheretherketone, polyetherimide, polyimide, fluororesin, polyamide, acrylic resin, and the like. 1 type(s) or 2 or more types can be used for these. In particular, a laminate in which two or more layers are laminated can also be used as the base material. For example, there is a laminate film in which a laminate comprising a polycarbonate layer/acrylic resin layer is used as a substrate film, and a cured film is formed on the acrylic resin layer of the substrate film.

The thickness of the substrate can be appropriately set according to the type of synthetic resin used, the application of the laminated film, etc., and can be, for example, about 30 to 1000 μm, but is not limited to this.

Curing Step In the curing step, a cured film is obtained by irradiating the coating film with an active energy ray. The active energy rays are not particularly limited, and examples thereof include electron beams (EB), ultraviolet rays (UV), infrared rays (IR), and the like. In the present invention, ultraviolet light can be preferably used because curing can be performed relatively easily. When using ultraviolet rays, the light source is not limited, and examples thereof include high-pressure mercury lamps, iron-doped metal halide lamps, gallium lamps, low-pressure mercury lamps, ultra-high-pressure mercury lamps, ultraviolet lasers, and LEDs. Therefore, it can be cured using a known or commercially available device equipped with these.

The ultraviolet irradiation conditions are, for example, a wavelength region of about 100 to 400 nm, an illuminance of about 80 to 1000 mW/cm ² , and an integrated light amount of about 100 to 5000 mJ/cm ^2. It is possible to irradiate ultraviolet rays having energy. is not limited to Ultraviolet irradiation can be performed using a known or commercially available UV irradiation device.

Although the temperature conditions for ultraviolet irradiation are not particularly limited, the temperature is usually within the range of 100° C. or lower. Therefore, for example, it should be preferably carried out even near room temperature (about 10 to 40 ° C.).

The thickness of the cured film varies depending on the application of the laminated film, the site of use, etc., and can generally be about 0.1 to 20 μm, but is not limited to this.

The laminated film of the present invention can be used as a pre-cure type film. Therefore, it is suitable for the method capable of integrating the laminated film of the present invention and the resin-containing molding, and at least a method capable of integrating the resin-containing molding at the same time as molding can be preferably employed. Here, the term "integrate" refers to bonding (preferably directly) and fixing the coating film of the composition of the present invention or its cured film and the resin-containing molding. Therefore, known molding methods such as insert molding, in-mold molding, and a bonding method (TOM (Three Dimension Overlay Method) method) can be suitably employed.

For example, as a representative example, when the cured film of the present invention and a resin-containing molding are integrated by insert molding, the method shown in FIG. 1 can be followed. That is, the laminated film 10 (that is, the laminated film of the present invention) in which the cured film 12 (hard coat layer) is laminated on the base film 11 is arranged between the male mold 21a and the female mold 21b. step (FIG. 1(a)), a second step (FIG. 1(b)) of pouring the molten resin 13a into the mold for injection molding, and after the resin is cured, the resin layer 13 (resin-containing molding) A method including a third step (FIG. 1(c)) of obtaining a molded body 30 (product) consisting of /base film 11/functional layer 12 can be suitably employed.

In this case, as in known insert molding, in addition to the above steps, a step of preheating and softening the laminated film or cured film prior to the first step, and a preliminary laminated film prior to the second step. A molding step, a step of cutting out (trimming) unnecessary portions, and the like may additionally be included.

In addition, although the cured film is used in the above method, it can be replaced with a coating film of the composition of the present invention (before curing). In this case, for example, a cured film may be obtained by curing the coating film by irradiating the molded body with ultraviolet rays or the like before or after removing the molded body from the mold.

The molded article thus obtained can be used as various products including interiors and exteriors of automobiles, home electric appliances and the like. More specifically, exterior materials (door handles, bumpers, front grilles, side moldings, wheel caps, mirror housing front undercovers, etc.) or interior materials (meter panels, shift knobs, switches, center consoles, door ornaments, etc.). Home appliances include, for example, refrigerators, washing machines, vacuum cleaners, personal computers, tablets, printers, multifunction peripherals, mobile phones, and audio products.

EXAMPLES Examples and comparative examples are shown below to describe the features of the present invention more specifically. However, the scope of the present invention is not limited to the examples. "%" in the examples indicates "% by weight" unless otherwise specified.

(1) Materials used Desmodur W: manufactured by Sumika Covestrourethane Co., Ltd., trade name, solid content concentration 100%, dicyclohexylmethane 4,4′-diisocyanate Desmodur I: Sumika Covestrourethane Co., Ltd. ) Product, trade name, solid content concentration 100%, isophorone diisocyanate 1,2-hexanediol (1,2-HD): manufactured by Tokyo Chemical Industry Co., Ltd., solid content concentration 100%
・ 1,2-octanediol (1,2-OD): manufactured by Tokyo Chemical Industry Co., Ltd., solid concentration 100%
・ 1,2-Decanediol (1,2-DD): manufactured by Tokyo Chemical Industry Co., Ltd., solid concentration 100%
・ 1,10-Decanediol (1,10-DD): Tokyo Chemical Industry Co., Ltd., solid content concentration 100%
・ 1,2-Hexadecanediol (1,2-HDD): Tokyo Chemical Industry Co., Ltd., solid content concentration 100%
・ Monoethanolamine: manufactured by Tokyo Chemical Industry Co., Ltd., solid content concentration 100%
· 4,4'-methylenebis (cyclohexylamine): manufactured by Tokyo Chemical Industry Co., Ltd., solid content concentration 100%
・HEAA: KJ Chemicals Co., Ltd., trade name, hydroxyethyl acrylamide, solid content concentration 100%
・ ACMO: KJ Chemicals Co., Ltd., trade name, acryloylmorpholine, solid content concentration 100%
Aronix M-306: manufactured by Toagosei Co., Ltd., trade name, solid content concentration 100%, mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (pentaerythritol triacrylate content 65 to 70%)
· MEK: methyl ethyl ketone · IC-184: manufactured by BASF Corporation, trade name, solid content concentration 100%, Irgacure 184 (photopolymerization initiator)
・PGM: propylene glycol monomethyl ether (organic solvent)
・BYK-UV3500: BYK Co., Ltd., trade name, solid content concentration 100%, acrylic-modified dimethyl silicone

(2) Examples and Comparative Examples (2-1) Synthesis of urethane urea compound
Production Example 1 of Urethane Urea Compound
Desmodur W (100 parts by weight), 1,2-HD (29 parts by weight) and MEK (162 parts by weight) were added to a 1 L eggplant flask and stirred at 80° C. for 4 hours. After that, 7 parts by weight of monoethanolamine was added to the stirred solution and stirred at 80° C. for 4 hours. Thereafter, Aronix M-306 (25 parts by weight) was added to the stirred solution and stirred at 80° C. for 4 hours to obtain urethane urea compound 1 having a radically polymerizable group. (Theoretical molecular weight: 6500, acrylic equivalent: 1083 g/eq, urethane equivalent: 244 g/eq, urea equivalent: 1383 g/eq)

Production Example 2 of Urethane Urea Compound
Desmodur W (100 parts by weight), 1,2-OD (37 parts by weight) and MEK (169 parts by weight) were added to a 1 L eggplant flask and stirred at 80° C. for 4 hours. After that, monoethanolamine (7 parts by weight) was added to the still stirred solution and stirred at 80° C. for 4 hours. Thereafter, Aronix M-306 (25 parts by weight) was added to the stirred solution and stirred at 80° C. for 4 hours to obtain a urethane urea compound 2 having a radically polymerizable group. (Theoretical molecular weight: 6900, acrylic equivalent: 1150 g/eq, urethane equivalent: 257 g/eq, urea equivalent: 1459 g/eq)

Production Example 3 of Urethane Urea Compound
Desmodur W (100 parts by weight), 1,2-DD (44 parts by weight) and MEK (176 parts by weight) were added to a 1 L eggplant flask and stirred at 80° C. for 4 hours. After that, monoethanolamine (7 parts by weight) was added to the still stirred solution and stirred at 80° C. for 4 hours. After that, Aronix M-306 (25 parts by weight) was added to the stirred solution and stirred at 80° C. for 4 hours to obtain urethane urea compound 3 having a radically polymerizable group. (Theoretical molecular weight: 7200, acrylic equivalent: 1200 g/eq, urethane equivalent: 269 g/eq, urea equivalent: 1525 g/eq)

Production Example 4 of Urethane Urea Compound
Desmodur W (100 parts by weight), 1,2-HDD (65 parts by weight) and MEK (197 parts by weight) were added to a 1 L eggplant flask and stirred at 80° C. for 4 hours. After that, monoethanolamine (7 parts by weight) was added to the still stirred solution and stirred at 80° C. for 4 hours. Thereafter, Aronix M-306 (25 parts by weight) was added to the stirred solution and stirred at 80° C. for 4 hours to obtain a urethane urea compound 4 having a radically polymerizable group. (Theoretical molecular weight: 8100, acrylic equivalent: 1350 g/eq, urethane equivalent: 304 g/eq, urea equivalent: 1721 g/eq)

Production Example 5 of Urethane Urea Compound
In the process of synthesizing urethane urea compound 3, 1,2-DD was changed to 1,10-DD, but in the same manner as in Production Example 3, insoluble matter precipitated. For this reason, the following tests were discontinued.

Production Example 6 of Urethane Urea Compound
Desmodur W (59 parts by weight), Desmodur I (50 parts by weight), ACMO (90 parts by weight), and HEAA (26 parts by weight) were added to a 1 L eggplant-shaped flask and stirred at room temperature for 2 hours. did. Monoethanolamine (7 parts by weight) was then added dropwise to the still stirred solution and stirred at room temperature for 3 hours. After that, a mixed solution of isopropyl alcohol (116 parts by weight) and 4,4'-methylenebis(cyclohexylamine) (37 parts by weight) was added to the stirred solution and stirred at room temperature for 3 hours to obtain a solution having a radically polymerizable group. However, a urethane urea compound 6 having no branched alkylene group was obtained. (Theoretical molecular weight: 1300, acrylic equivalent: 750 g/eq, urethane equivalent: 519 g/eq, urea equivalent: 481 g/eq)

(2-2) Production of curable resin composition (Part 1)
Examples 1-3 and Comparative Examples 1-2
As shown in Table 1, a urethane urea compound (MEK adjustment liquid with a solid content of 50%), a photopolymerization initiator (IC-184) and a solvent (PGM) are blended in a predetermined ratio (parts by mass) and mixed uniformly. Thus, a liquid curable composition having a solid concentration of 20.8% by weight was obtained.

Test example 1
Using the liquid curable composition obtained in each example and comparative example, it was applied onto a glass substrate by a bar coating method so that the film thickness after curing would be 3 μm. Then, the substrate coated with the curable resin composition was dried in an oven at 80° C. for 1 minute, and then irradiated with ultraviolet rays as active energy rays to cure the coating film made of the curable resin composition. The following physical properties were examined for the resulting cured film. The results are also shown in Table 1.

(1) Modulus of Elasticity The cured film on the glass base material was pushed by 0.3 μm with a nanoindentation tester to measure the modulus of elasticity.
(2) Presence or absence of cracks at the time of indentation The cured film on the glass substrate is indented to 100 mN with a nanoindentation tester. I checked if it exists. Then, it was determined that cracks had occurred when a bending point was observed, and that cracks had not occurred when a bending point was not observed.
For reference, FIG. 2 shows a contact stiffness-displacement graph when cracks do not occur (Example 1) and a contact stiffness-displacement graph when cracks occur (Comparative Example 2). Further, FIG. 3 shows the results of observing the appearance of the pushed-in portion with an optical microscope in the case of no cracks (Example 1) and the case of cracks (Comparative Example 2).

As shown in Table 1, urethane urea compound 6, which does not have a branched alkylene group, caused cracks in the indentation test, and thus the cured film was found to be brittle (Comparative Example 2).
On the other hand, it was confirmed that the urethane urea compounds 1 to 4 having a branched alkylene group or the like did not generate cracks and were rich in toughness (stretchability). , it was confirmed that the longer the branched chain length, the lower the elastic modulus. The reason for this is not clear, but it is thought that the longer the side chain (alkyl chain), which is a relatively soft site, the greater the steric hindrance, which inhibits intermolecular interactions (hydrogen bonds) and lowers the elastic modulus. .

(2-3) Production of curable resin composition (part 2)
Examples 4-6 and Comparative Examples 3-4
As shown in Table 2, the urethane urea compounds 1 to 4 and 6 synthesized above (MEK adjustment liquid with a solid content of 50%), an acrylic monomer (Aronix M-306), and a surface conditioner (BYK-UV-500 ), a photopolymerization initiator (IC-184), and a solvent (PGM) were blended in a predetermined ratio (parts by mass) to obtain a liquid curable composition having a solid concentration of 21% by weight.
Next, a coating film of the liquid curable resin composition was formed on the substrate. As a substrate, a laminate having a polycarbonate surface covered with an acrylic resin was used. Each curable resin composition was applied to the acrylic resin surface of the substrate by a bar coating method so that the film thickness after curing was about 3 μm. After drying the formed coating film in an oven at 80° C. for 1 minute, the curable resin composition was cured by irradiating the coating film with ultraviolet rays as active energy rays. Thus, a laminated film was produced.

Test example 2
The following properties of the laminated film obtained above were evaluated. The results are shown in Table 2, respectively.

(1) Coating Film Appearance Evaluation Using a haze meter corresponding to JIS K7136, the haze value measured was used to evaluate the transparency of the laminated film. If the haze value was 1% or less, it was judged to be transparent.
(2) Scratch resistance A load of 1000 g/cm ² was applied to steel wool #0000 placed on the surface of the cured film of the laminated film, and the steel wool was reciprocated on the cured surface 15 times. The haze value was measured using a haze meter similar to . A value (Δ value) was obtained by subtracting the haze value before the test from the measured haze value.
(3) Stretchability A tensile test (atmospheric temperature 190°C, sample size: 100 mm × 10 mm, distance between chucks: 50 mm, tensile speed: 500 mm / min) was performed, and the elongation at break was the point at which cracks occurred in the coating film by visual observation. As a degree, the stretchability of the formed film was evaluated.
(4) Chemical Resistance 0.2 g of a commercially available sunscreen cream (Ultra Sheer Dry Touch Sunscreen SPF100, manufactured by Johnson & Johnson) was applied to an area of 1 cm ² and allowed to stand at 80° C. for 1 hour. After that, the applied sunscreen cream was washed with a large amount of water, and the change in appearance of the cured film was visually observed.
High: No change in appearance is observed Medium: Changes such as whitening are observed in part of the appearance Low: Changes such as whitening are observed in the appearance

As is clear from the results in Table 2, when Examples 4 to 6 and Comparative Example 3 are compared, it can be seen that use of a urethane urea compound with a high elastic modulus provides higher scratch resistance.
A comparison of the urethane urea compound 1 and the urethane urea compound 6 reveals that even if the elastic modulus is high, the use of the brittle urethane urea compound 6 reduces the scratch resistance. The reason for this is thought to be that the coating film cracked when scratched, resulting in extra scratches.
Furthermore, a comparison of the urethane urea compounds 1 to 4 reveals that the shorter the branched chain length, the higher the chemical resistance due to the higher hydrogen bonding properties.

Claims (10)

A curable resin composition containing a urethane urea compound having a radically polymerizable group and a branched alkylene group having 6 to 10 carbon atoms. 2. The curable resin composition according to claim 1, wherein part or all of the urethane urea compound further has a divalent aliphatic cyclic group which may be substituted with an alkyl group. The curable resin composition according to claim 1 or 2, further comprising a (meth)acrylate compound and a photopolymerization initiator. The curable resin composition according to any one of claims 1 to 3, further comprising an organic solvent. The urethane urea compound has the following properties:
In a cured urethane urea film having a thickness of 3 μm or more produced by irradiating a urethane urea compound with ultraviolet rays having a wavelength of 250 nm to 350 nm at an integrated light amount of 500 mJ/cm ² ,
(1) The elastic modulus when the Berkovich indenter is pushed by 1/10 of the thickness at a speed of 0.08 μm / sec is 3.5 GPa to 5.4 GPa, and (2) the Berkovich indenter is 0.08 μm. There is no inflection point in the "contact stiffness-displacement graph" when pushing at a speed of / sec until the load reaches 100 mN,
The curable resin composition according to any one of claims 1 to 4, characterized by having A laminated film obtained by laminating a cured film of the curable resin composition according to any one of claims 1 to 5 on a substrate. 7. The laminated film according to claim 6, which is used for molding. A molded article having the cured film of the laminated film according to claim 6 or 7 on its outermost surface. A method for producing a urethane urea compound, comprising:
(a) a polyisocyanate compound (b) a diol compound having 6 to 10 carbon atoms and having at least one of a secondary hydroxyl group and a tertiary hydroxyl group (c) a primary alkanolamine and/or a secondary alkanolamine (d) A method for producing a urethane urea compound, comprising the step of reacting a starting material containing a hydroxyl group-containing (meth)acrylate compound. A urethane urea compound having the following properties:
In a cured urethane urea film having a thickness of 3 μm or more produced by irradiating a urethane urea compound with ultraviolet rays having a wavelength of 250 nm to 350 nm at an integrated light amount of 500 mJ/cm ² ,
(1) The elastic modulus when the Berkovich indenter is pushed by 1/10 of the thickness at a speed of 0.08 μm / sec is 3.5 GPa to 5.4 GPa, and (2) the Berkovich indenter is 0.08 μm. There is no inflection point in the "contact stiffness-displacement graph" when pushing at a speed of / sec until the load reaches 100 mN,
A urethane urea compound characterized by having

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