Sclerotic resin composition and laminated film using the same

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

[0001] The present invention relates to a novel curable resin composition and a laminated film using the same.

Background Art

[0002] For the interior or exterior of industrial products such as automobiles and home appliances, surface coating technology is applied to enhance their scratch resistance, design, etc. Conventionally, a method of separately forming a surface coat layer on a molded product pre-molded by injection molding or the like has been adopted. As a method of forming the surface coat layer in this case, in addition to the coating method, there is a water pressure transfer method in which a water-soluble film pre-printed is developed on the water surface to transfer the printed layer to the product.

[0003] As coating agents, 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.

[0004] For example, there is a polyurethane-urea resin composition obtained from a polyol (A), a polyisocyanate (B), a diamine (C), and a monoamine (M), wherein the polyol (A) contains a polycarbonate diol (a1) having a number average molecular weight of 2,200 to 6,000, the polyisocyanate (B) contains an alicyclic diisocyanate (b1), and the number average molecular weight of the polyurethane-urea resin composition is 30,000 to 90,000 (Patent Document 1).

[0005] For example, there is known a polyurethane-urea resin solution containing a polyurethane-urea resin (U) having a hydroxyl group-modified polyolefin (A), a polyisocyanate (B), and a chain extender (C) having a number average molecular weight or chemical formula weight of less than 500 as essential constituent monomers, and a solvent (S). In the hydroxyl group-modified polyolefin (A), the weight ratio of ethylene, which is a constituent monomer, 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 to 6,000 (Patent Document 2).

[0006] In recent years, insert molding and the like, in which a prefabricated cured film (pre-cure type) is used as a hard coat material and integrally molded together with a separately prepared resin composition, are becoming mainstream. For example, as shown in FIG. 1, after a laminated film 10 in which a cured film 12 (hard coat) is laminated on a base film 11 is disposed between a male mold 21a and a female mold 21b as a mold (FIG. 1(a)), molten resin 13a is poured into the mold and injection molded (FIG. 1(b)). After the resin is cured, unnecessary portions of the base film 11 are cut away (trimmed), and a molded article 30 (product) composed of a resin layer 13 / base film 11 / cured film 12 is taken out of the mold (FIG. 1(c)). In this way, a molded article having a hard coat by a cured film on the outermost surface can be provided.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] The pre-cure type film is further subjected to thermoforming (such as insert molding) after producing the cured film as described above, and thus it is necessary to have stretchability (formability) enough to withstand the thermoforming. That is, even when processed such as bent, a property is required that it can follow the processing without cracks or the like occurring on the surface. For example, as shown in the portion A of FIG. 1(b) above, particularly when the molded body 30 has a portion that bends in its thickness direction, it is necessary for the functional layer 12 to follow the base film 11 at that portion. If it cannot follow, problems such as the functional layer 12 peeling from the base film 11 over time or cracks occurring in the functional layer 12 will occur. For this reason, the functional layer 12 needs to have excellent adhesion to the base film and high stretchability and the like.

[0009] However, generally, when trying to increase the stretchability of a film, the hardness of the film decreases and the desired scratch resistance cannot be obtained. On the other hand, when improving the scratch resistance, the stretchability decreases and it becomes difficult to use as a pre-cure type film. Thus, in the pre-cure type film, although a film having both stretchability and scratch resistance is particularly desired, at present, such a film has not been developed yet because the two are physical properties that are mutually contradictory.

[0010] Therefore, 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.

Means for Solving the Problems

[0011] As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by adopting a composition having a specific composition, and has completed the present invention.

[0012] 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. The curable resin composition according to item 1 above, 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. The curable resin composition according to item 1 or 2 above, further containing a (meth)acrylate compound and a photopolymerization initiator. 4. The curable resin composition according to any one of items 1 to 3 above, further containing an organic solvent. 5. The urethane-urea compound has the following properties: In a urethane-urea cured film having a thickness of 3 μm or more formed by irradiating the urethane-urea compound with ultraviolet light having a wavelength of 250 nm to 350 nm at an integrated light amount of 500 mJ / cm 2 (1) The elastic modulus when a Berkovich indenter is pushed in by 1 / 10 of the thickness at a speed of 0.08 μm / second is 3.5 GPa to 5.4 GPa, and (2) There is no bending point in the "contact stiffness-displacement graph" when the Berkovich indenter is pushed in at a speed of 0.08 μm / second until a load of 100 mN is reached. The curable resin composition according to any one of items 1 to 4 above, characterized by having the above. The curable resin composition according to any one of items 1 to 4 above, characterized by having the above. 6. A laminated film obtained by laminating a cured film of the curable resin composition according to any one of items 1 to 5 above on a substrate. 7. The laminated film according to item 6 above, used for molding. 8. A molded article having the cured film of the laminated film according to item 6 or 7 above on its outermost surface. 9. A method for producing a urethane-urea compound, (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 hydroxyl group-containing (meth)acrylate compound A method for producing a urethane-urea compound, characterized by including a step of reacting a starting material containing 10. A urethane-urea compound having the following properties: In a urethane-urea cured film with a thickness of 3 μm or more formed by irradiating the urethane-urea compound with ultraviolet light having a wavelength of 250 nm to 350 nm and an integrated light quantity of 500 mJ / cm 2 (1) The elastic modulus is 3.5 GPa to 5.4 GPa when a Berkovich indenter is pushed in by 1 / 10 of the thickness at a speed of 0.08 μm / second, and (2) There is no inflection point in the "contact stiffness-displacement graph" when the Berkovich indenter is pushed in at a speed of 0.08 μm / second until a load of 100 mN is reached. A urethane-urea compound, characterized by having

Advantages of the Invention

[0013] 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. The cured film obtained from such a constituent resin composition can exhibit unique physical properties having both hardness and softness.

[0014] That is, the urethane-urea compound of the present invention has a structure in which a specific branched alkylene group and a radical polymerizable group are bonded in the urethane-urea structure. Therefore, even after curing, it exhibits desired stretchability and can be used in a molding process without any problems. In addition, the cured film after molding exhibits high scratch resistance and can exhibit excellent performance as a hard coat.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Figure 3

Explanation of Signs

[0016] 10 Laminated film 11 Base film 12 Cured film (cured layer) 13a Melted resin 13 Resin layer after curing 21a Male mold 21b Female mold 30 Molded body (product) A Bent part

Modes for Carrying Out the Invention

[0017] 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) is characterized by containing a urethane-urea compound (the compound of the present invention) having a radically polymerizable group and a branched alkylene group having 6 to 10 carbon atoms (hereinafter, also simply referred to as "branched alkylene group").

[0018] In the present invention, hereinafter, unless otherwise specified, an acryloyl group or a methacryloyl group is collectively referred to as a "(meth)acryloyl group". Further, an acryloyloxy group or a methacryloyloxy group is collectively referred to as a "(meth)acryloyloxy group". Furthermore, acrylate or methacrylate is collectively referred to as "(meth)acrylate", and acrylic acid or methacrylic acid is collectively referred to as "(meth)acrylic acid".

[0019] The compound of the present invention is a compound containing a urethane bond (-NHCOO-) and a urea bond (urea bond) (-NHCONH- or -NHCON<). The urethane bond and the urea bond may each independently have one or more.

[0020] Also, the urethane bond (hereinafter sometimes referred to as "A") and the urea bond (hereinafter sometimes referred to as "B") may be, for example, a) alternately bonded via an organic group R, b) a plurality of the same bonds form segments via an organic group R, and the segments themselves (i.e., the polyurethane structure and the polyurea structure) are bonded, c) both bonds are randomly bonded via an organic group R, or d) any of the cases including combinations of a) to c) above. The present invention encompasses any of the urethane-urea structures composed of a) to d) above.

[0021] In particular, in the case of a) above, for example -R 1 -A-R 2 -B- A structure in which one or more of these are bonded as a repeating unit can be mentioned.

[0022] In particular, in the case of b) above, for example -R 1 -A-R 2 -A-R 3 -A-R 4 -B-R 5 -B- -R 1 -A-R 2 -A-R 3 -B-R 4 -B-R 5 -B- -R 1 -A-R 2 -A-R 3 -A-R 4 -B-R 5 -B- -R 1 -A-R 2 -A-R 3 -A-R 4 -B-R 5 -B-R 6 -B- -R 1 -A-R 2 -A-R 3 -A-R 4 -B-R 5 -B-R 6 -B-R7 -B- Using this as a repeating unit, a structure in which one or more of these are bonded (wherein R 1 ~R 7 may be different organic groups from each other.) can be mentioned.

[0023] The organic group R bonded to the urethane bond or urea bond only needs to contain at least one radical polymerizable group and at least one branched alkylene group. Therefore, the organic group R itself may be a radical polymerizable group or a branched alkylene group.

[0024] Examples of the radical polymerizable group include, but are not limited to, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acrylamide group, vinyl group, allyl group, etc. These can also be used alone or in combination of two or more.

[0025] The number of radical polymerizable groups per molecule of the compound of the present invention is not limited, but usually may be about 2 to 10, and particularly preferably 6 to 10. Thereby, better curability can be exhibited.

[0026] The radical polymerizable group may be bonded to the end of the urethane-urea structure, but may also be bonded at a location other than the end. Note that the end 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.

[0027] The branched alkylene group has 6 to 10 carbon atoms. When the carbon number is 5 or less, it becomes difficult to dissolve in general-purpose solvents such as methyl ethyl ketone (MEK). Also, when the carbon number is 11 or more, the scratch resistance becomes low. Further, the carbon number of the carbon chain of only the branched portion is usually preferably 4 to 8. Furthermore, the number of branches is particularly preferably a branched alkylene group having 1 branch.

[0028] Therefore, specific examples of preferred branched alkylene groups include the following. These may be used alone or in combination of two or more. -CH 2 CH(C 4 H 9 )- -CH 2 CH(C 5 H 11 )- -CH 2 CH(C 6 H 13 )- -CH 2 CH(C 7 H 15 )- -CH 2 CH(C 8 H 17 )-

[0029] The number of branched alkylene groups per molecule of the compound of the present invention is not limited, but is usually about 4 to 23, and particularly preferably 7 to 18. Thereby, the solubility of the compound of the present invention in a general-purpose solvent (such as MEK) can be further enhanced.

[0030] The organic group R other than the radically polymerizable group and the branched alkylene group is not particularly limited, and examples thereof include 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, etc. In addition, a linear alkylene group not bonded to the branched alkylene group may be mentioned. These may be a combination of one kind or two or more kinds.

[0031] These organic groups R may or may not have a substituent. Examples of the substituent include the above-mentioned radically polymerizable group and branched alkylene group, and an alkyl group, etc. Therefore, for example, in the present invention, as the organic group R, a divalent aliphatic cyclic group which may be substituted with an alkyl group, etc. can be mentioned.

[0032] The number of carbon atoms of these organic groups R is not particularly limited, but is usually preferably about 2 to 15. When the organic group R has a substituent, it is the value including the number of carbon atoms of the substituent.

[0033] Specific examples of the organic group R include organic groups derived from the polyisocyanate compound as the starting material. For example, the following organic group R derived from dicyclohexylmethane 4,4'-diisocyanate a :

Chemical formula

[0034] Also, the following organic group R derived from isophorone diisocyanate b :

Chemical formula

[0035] The molecular weight of the compound of the present invention is not particularly limited, but from the viewpoint of stretchability, the number average molecular weight is usually preferably about 3000 to 10000, and particularly preferably 5000 to 8000. Therefore, the compound of the present invention may be in the form of an oligomer or a polymer. Further, the compound of the present invention can be, for example, 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 is not limited thereto.

[0036] The compound of the present invention has the following characteristics: In a urethane-urea cured film with a thickness of 3 μm or more formed by irradiating a urethane-urea compound with ultraviolet light having a wavelength of 250 nm to 350 nm and an integrated light amount of 500 mJ / cm 2 : (1) When a barcol indenter is pushed in by 1 / 10 of the thickness at a speed of 0.08 μm / second, the elastic modulus is 3.5 GPa to 5.4 GPa (Characteristic A), and (2) When the barco bit indenter is pushed in at a speed of 0.08 μm / second until a load of 100 mN is reached, there is no bending point in the "contact rigidity - displacement graph" (Characteristic B). It is desirable to have.

[0037] The above physical properties A and B are one of the 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 to form a cured film with excellent stretchability in the compound of the present invention. Mainly, physical property A is an indicator of the hardness of the cured film, and physical property B is an indicator of brittleness. The cured film to be evaluated contains the compound of the present invention, and more specifically, it is the physical property based on a liquid composition of 40.0% by weight of the compound of the present invention, 0.8% by weight of a photopolymerization initiator, and 59.2% by weight of propylene glycol monomethyl ether.

[0038] Characteristic A also indicates the ease of molding (or the difficulty of molding), and good moldability can be maintained within the above numerical range.

[0039] Characteristic B indicates that when the above - specified indenter is pushed into the cured film, no cracks occur in the part or its periphery. The presence of a bending point indicates that cracks have occurred around the pushed - in part. The cured film formed from the compound of the present invention has the property that cracks are less likely to occur even when a local force is applied from the outside. Therefore, for example, at the time of molding, even when a load such as bending is applied to the cured film, a molded body in which cracks and the like are less likely to occur on the surface of the cured film can be obtained.

[0040] Since the compound of the present invention satisfies both of the above characteristics A and B, it exhibits a certain durability even when subjected to a specific stress from the outside, and thus is suitable for the production of a cured film for molding (that is, a pre - cure type film).

[0041] Such compounds of the present invention can also preferably employ compounds produced by the following "Method for Producing Urethane Urea Compounds (1-2)". That is, the reaction product obtained by reacting at least the following components (a) to (d) can be preferably used as the compound of the present invention.

[0042] (1-2) Method for Producing Urethane Urea Compounds The method for producing the compound of the present invention is not particularly limited, but the following method can be preferably employed. That is, for example, a method including a step of reacting starting materials containing (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, and (d) a hydroxyl group-containing (meth)acrylate compound can preferably produce the compound of the present invention.

[0043] (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. For example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate; alicyclic polyisocyanates such as dicyclohexylmethane 4,4'-diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and trimers or multimers of isocyanate (adducts, biuret bodies, isocyanurate bodies, allophanate bodies) can be mentioned. These may be used alone or in combination of two or more. In the present invention, dicyclohexylmethane 4,4'-diisocyanate is particularly preferred.

[0044] (b) A diol compound having 6 to 10 carbon atoms and at least one hydroxyl group selected from secondary hydroxyl groups and tertiary hydroxyl groups The diol compound having 6 to 10 carbon atoms and at least one hydroxyl group selected from secondary hydroxyl groups and tertiary hydroxyl groups means that the total number of carbon atoms in the diol compound is 6 to 10, 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 bonded to a tertiary carbon atom).

[0045] Examples of the diol compound having 6 to 10 carbon atoms and at least one hydroxyl group selected from secondary hydroxyl groups and tertiary hydroxyl groups include, but are not limited to, 1,2 - hexanediol, 1,2 - octanediol, 1,2 - 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, etc. These can be used alone or in combination of two or more. In particular, in the present invention, the following formula:

Chemical formula

[0046] The blending amount of the above diol compound is not particularly limited, but usually it is preferably about 0.5 to 0.9 moles, more preferably 0.6 to 0.8 moles, per 1 mole of the above polyisocyanate compound.

[0047] (c) Primary alkanolamine and / or secondary alkanolamine The primary alkanolamine and / or secondary alkanolamine is not particularly limited as long as it is a compound having a primary amino group or a secondary amino group and a hydroxyl group. Examples include 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 alone or in combination of two or more. In the present invention, monoethanolamine is particularly preferred.

[0048] The blending amount of the above alkanolamine is not particularly limited, but usually it is preferably about 0.05 to 0.45 mol, more preferably 0.15 to 0.35 mol, per 1 mol of the above polyisocyanate compound.

[0049] Also, the mixing molar ratio of the diol having a branched structure and the alkanolamine is not limited, but usually it is preferably about 1.5:1 to 9:1. By setting it within this range, more excellent chemical resistance and good solvent solubility can be obtained.

[0050] (d) Hydroxyl - containing (meth)acrylate compound The (meth)acrylate compound containing a hydroxyl group is not particularly limited as long as it has one or more hydroxyl groups. For example, hydroxyalkyl (meth)acrylates having 1 to 16 carbon atoms (preferably 1 to 12 carbon atoms) in the alkyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate; compounds having one ethylenically unsaturated group such as 2-hydroxyethyl (meth)acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth)acrylate, fatty acid-modified glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate; compounds having two ethylenically unsaturated groups such as glycerin di(meth)acrylate, 2-hydroxy-3-(meth)acryloyl-oxypropyl (meth)acrylate; compounds having three or more ethylenically unsaturated groups such as 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, succinic acid-modified pentaerythritol tri(meth)acrylate can be mentioned.

[0051] The blending amount of the above acid group-containing (meth)acrylate compound is not particularly limited, but usually it is preferably about 0.02 to 0.2 mol, more preferably 0.05 to 0.15 mol, per 1 mol of the above polyisocyanate compound.

[0052] The reaction in the production method of the present invention is preferably a liquid-phase reaction in an organic solvent. As the organic solvent, for example, 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; ether solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, propylene glycol 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, from the viewpoint of adhesion and the like, it is preferable to use a ketone solvent.

[0053] In the present invention, it is preferable that each component forms a solution by dissolving in an organic solvent. By forming a solution in which all components are dissolved, a good coating film can be formed by coating.

[0054] When using an organic solvent, the amount of the organic solvent used is not limited. For example, within the range where the solid content is 10 to 90% by weight, it can be appropriately set according to the type of components used, the desired viscosity, and the like.

[0055] In the production method of the present invention, after dissolving these components in an organic solvent, a predetermined reaction step may be carried out.

[0056] The reaction conditions are not limited, but are preferably as follows. First, as the order of reacting each component, in particular, (A) a step of reacting (a) a polyisocyanate compound and (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, (B) a step of adding (c) a primary alkanolamine and / or a secondary alkanolamine to the obtained reaction solution and reacting, and (C) a step of adding (d) a hydroxyl group-containing (meth)acrylate compound to the obtained reaction solution and reacting can be preferably adopted. Thereby, a urethane urea structure can be formed more reliably, and a desired organic group (that is, a branched alkylene group and a radically polymerizable group) can be imparted to the urethane urea structure.

[0057] The reaction temperature is not particularly limited, but usually it may be about 20 to 110 °C, and particularly preferably 60 to 90 °C.

[0058] The finally obtained compound of the present invention can usually be obtained in a liquid form and can be used as the composition of the present invention as it is. In addition, the composition of the present invention can also be prepared by a) adjusting the solid content concentration as necessary, or b) further mixing other components as necessary.

[0059] (2) The 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 can take the form of a solution in which the compound of the present invention is dissolved in an organic solvent.

[0060] In the composition of the present invention, additives other than the compound of the present invention may be contained as necessary, but it is particularly preferable to further contain a (meth)acrylate compound and a photopolymerization initiator. Thereby, higher scratch resistance and the like can be obtained.

[0061] (Meth)acrylate compound (Meth)acrylate compounds are not limited as long as they can contribute to curing. For example, various compounds such as alkyl group-containing (meth)acrylate compounds, aromatic ring-containing (meth)acrylate compounds, ether chain-containing (meth)acrylate compounds, and nitrogen-containing (meth)acrylate compounds can be used. These (meth)acrylate compounds can be either compounds containing a hydroxyl group or compounds not containing a hydroxyl group. These can be used alone or in combination of two or more.

[0062] Examples of the above alkyl group-containing (meth)acrylate compounds include linear or branched alkyl group-containing (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 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, and isostearyl (meth)acrylate.

[0063] Examples of the above 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.

[0064] Examples of the alicyclic structure-containing (meth)acrylate compound include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl methacrylate, cyclohexane spiro-2-(1,3-dioxolan-4-yl)methyl (meth)acrylate, 3-ethyl-3-oxetanyl methyl (meth)acrylate, 1-adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and the like.

[0065] Examples of the ether chain-containing (meth)acrylate compound include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-isopropoxyethyl methacrylate, 3-methoxybutyl (meth)acrylate, 2-butoxyethyl (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, methoxypolyethylene glycol (meth)acrylate, octoxypolyethylene glycol-polypropylene glycol-mono(meth)acrylate, lauroxypolyethylene glycol mono(meth)acrylate, stearoxypolyethylene glycol mono(meth)acrylate, and the like.

[0066] Examples of the nitrogen-containing (meth)acrylate compound include t-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, pentamethylpiperidinyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, acryloylmorpholine, dimethylaminoethyl methacrylate quaternary compound, dimethylacrylamide, isopropylacrylamide, and the like.

[0067] Examples of the salicylic acid-containing (meth)acrylate compound 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. In addition, monomers having a plurality of (meth)acryloyl groups such as pentaerythritol tetra(meth)acrylate are also included.

[0068] Photoinitiator The photoinitiator is not particularly limited as long as it can initiate polymerization by active energy rays such as electron beam (EB), ultraviolet ray (UV), and infrared ray (IR). For example, dimethyl-2,2'-azobis(2-methylpropionate), 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 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-dimethylamino-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. These photoinitiators can also be known or commercially available ones.

[0069] The content of the photoinitiator can be appropriately set according to the type of the photoinitiator used and the like. Usually, it may be in the range of about 1 to 10% by weight in 100% by weight of the composition of the present invention (solid content), and particularly preferably 1 to 5% by weight from the viewpoint of curability.

[0070] 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 interfere with the effects of the present invention. For example, crosslinking agents, inorganic fine particles (oxide fine particles such as silica, alumina, titania, zirconia, etc.), antifouling agents (slip agents), surface modifiers (silicone-based compounds, fluorine-based compounds), ultraviolet absorbers, light stabilizers, dispersants (surfactants), wetting agents, thickeners, antioxidants, polymerization inhibitors, polymerization regulators, colorants, and the like can be mentioned.

[0071] It is preferable that the curable composition of the present invention dissolves each component in an organic solvent to form a solution. As the organic solvent, for example, 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; ether solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether; and various organic solvents such as aromatic solvents such as toluene and xylene can be used. The amount of the organic solvent 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.

[0072] The composition of the present invention can be prepared by mixing the above-described components so as to be uniform. Also, the mixing order of each component is not limited. The temperature and the like during mixing are not limited either, and for example, it can be carried out under normal temperature and normal pressure. The mixing can be carried out using known or commercially available devices such as mixers and kneaders.

[0073] 2. Laminated Film The present invention includes a laminated film formed by laminating a cured film of the composition of the present invention on a substrate. That is, the present invention includes a laminated film including a substrate and a cured film of the composition of the present invention formed thereon.

[0074] 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 is usually desirably about 0.1 to 5%.

[0075] Also, regarding the cured film, it 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 is usually desirably about 0.1 to 5%.

[0076] As long as the cured film is on the outermost surface during use, the laminated film of the present invention may be laminated with other layers as needed. For example, various layers such as an antistatic layer, a moisture barrier layer, an adhesive layer, an anchor coat layer, a primer layer, a printing layer, and an antireflection layer can be mentioned.

[0077] The thickness of the laminated film can be appropriately set according to the type of the substrate used, the use of the laminated film, etc., and can be, for example, about 30 to 1000 μm, but is not limited thereto.

[0078] Since the laminated film of the present invention particularly has excellent stretchability of the cured film, it can be suitably used as a material for manufacturing a desired molded article by molding the cured film. Therefore, it is optimal as a film used for molding. More specifically, although it is a cured film having excellent scratch resistance, it has high stretchability. As a result, even if the laminated film including the cured film is molded, it can be deformed into a desired shape, and thus a molded article substantially free of surface cracks and the like can be manufactured. Thereby, it becomes possible to provide a product having an excellent hard coat on the surface of various molded articles.

[0079] The method for manufacturing the laminated film of the present invention is not particularly limited. For example, it can preferably be manufactured by a method including 1) a step of forming a coating film of the composition of the present invention on a substrate (coating film forming step) and 2) a step of forming a cured film by irradiating the coating film with active energy rays (curing step).

[0080] Coating film forming step In the coating film forming step, a coating film of the composition of the present invention is formed on a substrate. The method for forming the coating film is not particularly limited. For example, it can be formed by applying the liquid composition of the present invention onto the substrate. The coating method is not particularly limited. For example, in addition to methods such as brush coating, spraying, dipping, doctor blade, bar coater, etc., printing methods such as screen printing, gravure printing, offset printing method, etc. can also be adopted.

[0081] For the coating film, a drying step can be carried out as necessary. The drying method is not restrictive. For example, in addition to natural drying, drying by heating can also be adopted. The heating temperature should be within a range that does not adversely affect the substrate. For example, it can be heated at about 70 to 120 °C, but it is not limited to this.

[0082] As the base material, for example, films made of various materials such as synthetic resins, rubbers, and metals can be preferably used. In particular, examples of synthetic resins include polyester-based (such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyolefin-based (such as polyethylene, polypropylene, etc.), cellulose-based (such as cellophane, diacetyl cellulose, triacetyl cellulose, etc.), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polyether ether ketone, polyether imide, polyimide, fluororesin, polyamide, acrylic resin, etc. These can be used alone or in combination of two or more. In particular, as the base material, a laminate in which two or more layers are laminated can also be used. For example, a laminated film in which a cured film is formed on the acrylic resin layer of the base film using a laminate composed of a polycarbonate layer / acrylic resin layer as the base film can be mentioned.

[0083] The thickness of the base material can be appropriately set according to, for example, the type of synthetic resin used, the use of the laminated film, etc., and can be, for example, about 30 to 1000 μm, but is not limited thereto.

[0084] Curing process In the curing process, a cured film is obtained by irradiating the coating film with active energy rays. The active energy rays are not particularly limited, and examples include electron beams (EB), ultraviolet rays (UV), infrared rays (IR), etc. In the present invention, ultraviolet rays can be preferably used particularly in terms of being able to carry out curing relatively easily. When using ultraviolet rays, the light source is not limited either, and examples include high-pressure mercury lamps, iron-doped metal halide lamps, gallium lamps, low-pressure mercury lamps, ultra-high-pressure mercury lamps, ultraviolet lasers, LEDs, etc. Therefore, curing can be carried out using a known or commercially available device equipped with these.

[0085] The irradiation conditions for ultraviolet rays are, for example, in a wavelength range of about 100 to 400 nm, and the illuminance is 80 to 1000 mW / cm 2Degree, integrated light quantity of 100 to 5000 mJ / cm 2 It is possible to irradiate ultraviolet rays having energy of this degree or more, but not limited thereto. The ultraviolet ray irradiation can be carried out using a known or commercially available UV irradiation device.

[0086] In addition, the temperature conditions for ultraviolet ray irradiation are not particularly limited, but usually may be within the range of 100°C or lower. Therefore, for example, it can be preferably carried out even near room temperature (about 10 to 40°C).

[0087] The thickness of the cured film varies depending on the use of the laminated film, the use site, etc., and generally can be about 0.1 to 20 μm, but is not limited thereto.

[0088] The laminated film of the present invention can be used as a pre-cure type film. Therefore, it is suitable for a method capable of integrating the laminated film of the present invention and a resin-containing molded article, and a method capable of integrating at least simultaneously with the molding of the resin-containing molded article can be preferably employed. Here, "integration" means joining and fixing (preferably directly) the coating film of the composition of the present invention or its cured film and the resin-containing molded article. Therefore, for example, known molding methods such as insert molding, in-mold molding, and bonding method (TOM (Three dimension Overlay Method) method) can be preferably employed.

[0089] For example, when integrating the cured film of the present invention and a resin-containing molded article by insert molding as a representative example, it can be carried out according to the method shown in FIG. 1. That is, a first step of disposing a laminated film 10 (that is, the laminated film of the present invention) having a cured film 12 (hard coat layer) laminated on a base film 11 between a male mold 21a and a female mold 21b of a mold (FIG. 1(a)), a second step of injecting molten resin 13a into the mold and performing injection molding (FIG. 1(b)), and a third step of obtaining a molded article 30 (product) composed of a resin layer 13 (resin-containing molded article) / base film 11 / functional layer 12 after the resin is cured (FIG. 1(c)) can be preferably employed.

[0090] In this case, similar to the known insert molding, in addition to the above steps, prior to the first step, a step of preheating and softening the above-mentioned laminated film or cured film, a step of preforming the laminated film in advance prior to the second step, a step of cutting off (trimming) unnecessary portions, etc. may also be additionally included.

[0091] Also, although a cured film is used in the above method, it can also be replaced with a coating film of the composition of the present invention (before curing). In this case, for example, before or after taking out the molded body from the mold, the coating film may be cured by irradiating the molded body with ultraviolet rays or the like to obtain a cured film.

[0092] The molded body thus obtained can be used as various products including interior or exterior decorations of automobiles, home appliances, etc. More specifically, exterior materials (door handles, bumpers, front grills, side moldings, wheel caps, mirror housings, front under covers, etc.) or interior materials (meter panels, shift knobs, switches, center consoles, door ornaments, etc.) of various vehicles such as automobiles, railways, and airplanes can be mentioned. Also, examples of home appliances include refrigerators, washing machines, vacuum cleaners, personal computers, tablets, printers, multifunction devices, mobile phones, audio products, etc.

Examples

[0093] Examples and comparative examples are shown below to more specifically explain the features of the present invention. However, the scope of the present invention is not limited to the examples. “%” in the examples indicates “% by weight” unless otherwise specified.

[0094] (1) Regarding the materials used · Desmodur W: manufactured by Sumika Covestro Urethane Co., Ltd., trade name, solid content concentration 100%, dicyclohexylmethane 4,4'-diisocyanate · Desmodur I: product of Sumika Covestro Urethane Co., Ltd., 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 content concentration 100% · 1,2 - Decanediol (1,2 - DD): Manufactured by Tokyo Chemical Industry Co., Ltd., solid content 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: Manufactured by KJ Chemicals Co., Ltd., trade name, hydroxyethylacrylamide, solid content concentration 100% · ACMO: Manufactured by 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 (content of pentaerythritol triacrylate 65 - 70%) · MEK: Methyl ethyl ketone · IC - 184: Manufactured by BASF Co., Ltd., trade name, solid content concentration 100%, Irgacure 184 (photoinitiator) · PGM: Propylene glycol monomethyl ether (organic solvent) · BYK - UV3500: BYK Co., Ltd., trade name, solid content concentration 100%, acrylic - modified dimethyl silicone

[0095] (2) Regarding Examples and Comparative Examples (2 - 1) Synthesis of urethane - urea compound Production Example 1 of Urethane Urea Compound To a 1-L eggplant flask, Desmodur W (100 parts by weight), 1,2-HD (29 parts by weight), and MEK (162 parts by weight) were added, and the mixture was stirred at 80 °C for 4 hours. Then, 7 parts by weight of monoethanolamine was added to the stirred solution, and the mixture was stirred at 80 °C for 4 hours. Then, Aronix M-306 (25 parts by weight) was added to the stirred solution, and the mixture was stirred at 80 °C for 4 hours to obtain a urethane-urea compound 1 having a radical polymerizable group. (Theoretical molecular weight: 6500, acrylic equivalent: 1083 g / eq, urethane equivalent: 244 g / eq, urea equivalent: 1383 g / eq)

[0096] Production Example 2 of Urethane Urea Compound To a 1-L eggplant flask, Desmodur W (100 parts by weight), 1,2-OD (37 parts by weight), and MEK (169 parts by weight) were added, and the mixture was stirred at 80 °C for 4 hours. Then, 7 parts by weight of monoethanolamine was added to the stirred solution, and the mixture was stirred at 80 °C for 4 hours. Then, Aronix M-306 (25 parts by weight) was added to the stirred solution, and the mixture was stirred at 80 °C for 4 hours to obtain a urethane-urea compound 2 having a radical polymerizable group. (Theoretical molecular weight: 6900, acrylic equivalent: 1150 g / eq, urethane equivalent: 257 g / eq, urea equivalent: 1459 g / eq)

[0097] Production Example 3 of Urethane Urea Compound To a 1-L eggplant flask, Desmodur W (100 parts by weight), 1,2-DD (44 parts by weight), and MEK (176 parts by weight) were added, and the mixture was stirred at 80 °C for 4 hours. Then, 7 parts by weight of monoethanolamine was added to the stirred solution, and the mixture was stirred at 80 °C for 4 hours. Then, Aronix M-306 (25 parts by weight) was added to the stirred solution, and the mixture was stirred at 80 °C for 4 hours to obtain a urethane-urea compound 3 having a radical polymerizable group. (Theoretical molecular weight: 7200, acrylic equivalent: 1200 g / eq, urethane equivalent: 269 g / eq, urea equivalent: 1525 g / eq)

[0098] Production Example 4 of Urethane Urea Compound To a 1-L eggplant flask, Desmodur W (100 parts by weight), 1,2-HDD (65 parts by weight), and MEK (197 parts by weight) were added, and the mixture was stirred at 80 °C for 4 hours. Then, monoethanolamine (7 parts by weight) was added to the stirred solution, and the mixture was stirred at 80 °C for 4 hours. Then, Aronix M-306 (25 parts by weight) was added to the stirred solution, and the mixture was 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)

[0099] Production Example 5 of Urethane Urea Compound In the synthesis step of the urethane-urea compound 3, the same operations as in Production Example 3 were carried out except that 1,2-DD was changed to 1,10-DD, and insolubles precipitated. Therefore, the following tests were discontinued.

[0100] Production Example 6 of Urethane Urea Compound To a 1-L eggplant flask, 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, and the mixture was stirred at room temperature for 2 hours. Then, monoethanolamine (7 parts by weight) was added dropwise to the stirred solution, and the mixture was stirred at room temperature for 3 hours. Then, 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 the mixture was stirred at room temperature for 3 hours to obtain a urethane-urea compound 6 having a radically polymerizable group but not having a branched alkylene group. (Theoretical molecular weight: 1300, acrylic equivalent: 750 g / eq, urethane equivalent: 519 g / eq, urea equivalent: 481 g / eq)

[0101] (2-2) Production of the curable resin composition (Part 1) Examples 1 to 3 and Comparative Examples 1 to 2 As shown in Table 1, a urethane-urea compound (MEK-adjusted solution with a solid content of 50%), a photopolymerization initiator (IC-184), and a solvent (PGM) were blended at a predetermined ratio (parts by mass) and uniformly mixed to obtain a liquid curable composition having a solid content concentration of 20.8% by weight.

[0102] Test Example 1 Using the liquid curable compositions obtained in each of the examples and comparative examples, they were applied onto a glass substrate by a bar coating method so that the film thickness after curing became 3 μm. Then, after drying the substrate coated with the curable resin composition in an oven at 80 °C for 1 minute, ultraviolet rays were irradiated as active energy rays to cure the coating film composed of the curable resin composition. Regarding the obtained cured film, the following physical properties were examined. The results are also shown in Table 1.

[0103] (1) Elastic modulus The cured film on the glass substrate was indented by 0.3 μm with a nanoindentation tester to measure the elastic modulus. (2) Presence or absence of cracks during indentation The cured film on the glass substrate was indented with a nanoindentation tester until it reached 100 mN, and it was confirmed whether there was an inflection point in the graph of the calculated contact stiffness and indentation depth (contact stiffness - displacement graph). And when an inflection point was recognized, it was determined that cracks had occurred, and when no inflection point was recognized, it was determined that no cracks had occurred. For reference, the contact stiffness - displacement graph when no cracks occurred (Example 1) and the contact stiffness - displacement graph when cracks occurred (Comparative Example 2) are shown in FIG. 2. Also, the results of observing the appearance of the indented portion when no cracks occurred (Example 1) and when cracks occurred (Comparative Example 2) with an optical microscope are shown in FIG. 3.

[0104]

Table 1

[0105] As shown in Table 1, since cracks occurred in the urethane - urea compound 6 having no branched alkylene group in the indentation test, it was found that the cured film was 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). However, when comparing the urethane-urea compounds 1 to 3 with the urethane-urea compound 4, it was confirmed that the elastic modulus decreased as the branched chain length increased. The reason is not clear, but it is considered that when the side chain (alkyl chain), which is a relatively soft part, becomes longer, the steric hindrance increases, inhibiting the intermolecular interaction (hydrogen bond) and lowering the elastic modulus.

[0106] (2-3) Production of curable resin composition (Part 2) Examples 4 to 6 and Comparative Examples 3 to 4 As shown in Table 2, the urethane-urea compounds 1 to 4 and 6 (MEK-adjusted solution with a solid content of 50%) synthesized above, an acrylic monomer (Allonix M-306), a surface conditioner (BYK-UV-500), a photopolymerization initiator (IC-184), and a solvent (PGM) were blended at a predetermined ratio (parts by mass) to obtain a liquid curable resin composition with a solid content concentration of 21% by weight. Next, a coating film of the liquid curable resin composition was formed on a substrate. As the substrate, a laminate in which the polycarbonate surface was covered with an acrylic resin was used. Each curable resin composition was applied to the acrylic resin surface of the substrate by the bar coating method so that the finally obtained cured film thickness would be about 3 μm. Then, 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. In this way, a laminated film was produced.

[0107] Test Example 2 The laminated film obtained above was evaluated for the following properties. The results are shown in Table 2 respectively.

[0108] (1) Coating film appearance evaluation Using a haze meter corresponding to JIS K7136, the transparency of the laminated film was evaluated based on the measured haze value. If the haze value was 1% or less, it was judged as transparent. (2) Abrasion resistance A load of 1000 g / cm was applied onto the steel wool placed on the surface of the cured film of the laminated film #0000 2 After that, the steel wool was reciprocated 15 times on the cured surface, and then the haze value was measured using the same haze meter as in (1) above. The value (Δ value) obtained by subtracting the haze value before the test from the measured haze value was determined. (3) Elongation A tensile test (atmospheric temperature: 190 °C, sample dimensions: 100 mm × 10 mm, distance between chucks: 50 mm, tensile speed: 500 mm / min) was carried out, and the elongation of the formed film was evaluated by visually observing the point at which cracks occurred in the coating film as the elongation at the break point. (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 left standing at 80 °C for 1 hour. Then, the applied sunscreen cream was washed with a large amount of water, and the change in the appearance of the cured film was observed visually. High: No change is observed in the appearance Medium: Changes such as whitening are observed in part of the appearance Low: Changes such as whitening are observed in the appearance

[0109]

Table 2

[0110] As is clear from the results in Table 2, when comparing Examples 4 to 6 with Comparative Example 3, it can be seen that using a urethane-urea compound with a higher elastic modulus results in higher scratch resistance. Also, when comparing Urethane-urea Compound 1 and Urethane-urea Compound 6, it can be seen that even if the elastic modulus is high, using the brittle Urethane-urea Compound 6 results in lower scratch resistance. This is presumably because the coating film cracks during scratching, causing additional damage. Furthermore, when comparing Urethane-urea Compounds 1 to 4, it can be seen that the shorter the branched chain length, the higher the hydrogen bonding property and thus the higher the chemical resistance.

Claims

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, wherein the branched alkylene group is at least one selected from the group consisting of —CH2CH(C4H9)—, —CH2CH(C5H11)—, —CH2CH(C6H13)—, —CH2CH(C7H15)—, and —CH2CH(C8H17)—. Curable resin composition.

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.

3. The curable resin composition according to claim 1 or 2, further containing a (meth)acrylate compound and a photopolymerization initiator.

4. The curable resin composition according to any one of claims 1 to 3, further containing an organic solvent.

5. The urethane-urea compound has the following properties: A liquid curable composition containing 40% by weight of a methyl ethyl ketone adjusting solution containing 50% by solid content of a urethane urea compound, 0.8% by weight of a photoinitiator, and 59.2% by weight of propylene glycol monomethyl ether is used, applied onto a glass substrate by the bar coating method, and after drying the substrate coated with the composition in an oven at 80 °C for 1 minute, ultraviolet rays with a wavelength of 250 nm to 350 nm are irradiated with an integrated light quantity of 500 mJ / cm ２ In a urethane urea cured film with a thickness of 3 μm produced by irradiation, (1) The elastic modulus when a Berkovich indenter is pushed in by 1 / 10 of the thickness at a speed of 0.08 μm / second is 3.5 GPa to 5.4 GPa, and (2) There is no inflection point in the "contact stiffness-displacement graph" when a Berkovich indenter is pushed in at a speed of 0.08 μm / second until a load of 100 mN is reached. The curable resin composition according to any one of claims 1 to 4, characterized by having the above properties.

6. The urethane-urea compound is (a) number average molecular weight: 3000 to 10000, (b) acrylic equivalent: 1000 to 1500 g / eq, (c) urethane equivalent: 200 to 400 g / eq and (d) urea equivalent: 1000 to 2000 g / eq The curable resin composition according to any one of claims 1 to 5, which satisfies all of the above.

7. A laminated film obtained by laminating a cured film of the curable resin composition according to any one of claims 1 to 6 on a substrate.

8. The laminated film according to claim 7, which is used for molding.

9. A molded article having the cured film of the laminated film according to claim 7 or 8 on the outermost surface.

10. 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 hydroxyl group of a secondary hydroxyl group and a tertiary hydroxyl group (c) a primary alkanolamine and / or a secondary alkanolamine (d) a hydroxyl group-containing (meth)acrylate compound A method for producing a urethane-urea compound, comprising a step of reacting a starting material containing

11. The production method according to claim 10, wherein the diol compound is at least one selected from 1,2-hexanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 3,3-dimethyl-1,2-butanediol, 2,3-dimethyl-2,3-butanediol, 2,3-dimethyl-1,2-butanediol, and 2-methyl-2,4-pentanediol.

12. A urethane-urea compound having a radically polymerizable group and at least one selected from the group consisting of -CH2CH(C4H9)-, -CH2CH(C5H11)-, -CH2CH(C6H13)-, -CH2CH(C7H15)-, and -CH2CH(C8H17)- as a branched alkylene group having 6 to 10 carbon atoms, and having the following characteristics: Using a liquid curable composition containing 40% by weight of a methyl ethyl ketone adjusting solution containing 50% by solid content of a urethane urea compound, 0.8% by weight of a photoinitiator, and 59.2% by weight of propylene glycol monomethyl ether, applying it onto a glass substrate by the bar coating method, drying the substrate coated with the composition in an oven at 80 °C for 1 minute, and then irradiating with ultraviolet rays having a wavelength of 250 nm to 350 nm with an integrated light quantity of 500 mJ / cm ２ In a urethane urea cured film with a thickness of 3 μm formed by irradiation, (1) The elastic modulus is 3.5 GPa to 5.4 GPa when a Berkovich indenter is pushed in by 1 / 10 of the thickness at a speed of 0.08 μm / second, and (2) There is no bending point in the "contact stiffness-displacement graph" when a Berkovich indenter is pushed in at a speed of 0.08 μm / second until a load of 100 mN is reached. A urethane-urea compound, characterized by having

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