JP2015071665A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition, a cured material of which shows an excellent antiblocking property and which can form fine irregularities on a surface thereof after coating, a height of the irregularities further being able to be regulated.SOLUTION: A curable composition comprises a (meth)acrylic polymer and a dendrimer (meth)acrylate. A cured material obtained shows an excellent antiblocking property. The composition forms fine irregularities on a surface thereof after coating and, further, a height of the irregularities can be regulated.

Description

  The present invention relates to a curable composition. More specifically, the present invention is excellent in anti-blocking property, forms fine irregularities on the surface after coating, and further cures the height of the irregularities. The present invention relates to a sex composition.

  A thermoplastic resin film typified by a polyethylene terephthalate (PET) film may be provided with a hard coating on its surface, and may be stored in a roll shape so as not to be bulky. However, when a hard-coated film is wound into a roll, the hard coat surfaces may contact each other or the hard coat surface and another film surface may cause unexpected blocking.

  As a method for preventing such blocking, for example, adding inorganic fine particles to the hard coat layer and setting the layer surface to a specific roughness has been proposed (see Patent Document 1). Further, by using a curable resin composition containing a resin and a monomer having a specific unsaturated double bond group containing an alkylene oxide unit having 2 to 4 carbon atoms, the resin is precipitated by phase separation after coating, It has been reported that fine irregularities can be formed to prevent blocking (see Patent Document 2). On the other hand, an invention of an ultraviolet curable coating that focuses on the solubility parameter (SP value) of an acrylic resin has been reported. Polypropylene, polycarbonate, etc. are obtained by segregating a low SP value acrylic resin on the surface of the hard coat layer. It is described that the affinity (adhesiveness) with various plastics can be improved (see Patent Document 3).

JP 2004-42653 A JP 2010-163535 A JP 2002-348498 A

  A curable resin composition capable of forming fine irregularities on the surface by phase separation after coating as described in Patent Document 2 is suitable as a hard coat layer capable of preventing blocking. Furthermore, if the height of the unevenness can be controlled, it can lead to adjustment of the coefficient of friction of the hard coat layer and the like, which can be an important technique for further expanding the applicability of the curable composition. In particular, if this unevenness can be made higher, the friction coefficient of the hard coat layer can be lowered, and the slipperiness of the hard coat layer surface can be improved.

  According to the study by the present inventors, for example, when a curable composition containing a resin such as a (meth) acrylic polymer and a polyfunctional (meth) acrylate such as dipentaerythritol hexaacrylate is cured, It has been found that fine irregularities can be formed on the surface of the cured product, and blocking can be prevented by these irregularities. However, in such a curable composition containing a polyfunctional (meth) acrylate such as dipentaerythritol hexaacrylate, the surface roughness of the unevenness (the height of the unevenness) is limited, and the height of the unevenness is controlled. It has been found that there is a problem in that it is necessary to form larger irregularities.

  That is, the present invention provides a curable composition in which the resulting cured product is excellent in antiblocking properties, forms fine irregularities on the surface after application, and can control the height of the irregularities. Is an issue.

  As a result of intensive studies to solve the above problems, the present inventors have found that a curable composition containing a (meth) acrylic polymer and a dendrimer (meth) acrylate is a cured product having excellent antiblocking properties. The present invention has been completed by finding that the composition is capable of being applied and forming a concavo-convex surface on the surface after coating, and that the height of the concavo-convex surface can be controlled. That is, the gist of the present invention is as follows.

[1] A curable composition comprising the following component (A) and the following component (B).
Component (A): (meth) acrylic polymer having a weight average molecular weight (Mw) exceeding 5,000 Component (B): dendrimer (meth) acrylate having a weight average molecular weight (Mw) of 5,000 or less

[2] The curable composition according to [1], wherein the SP value of the component (A) and the SP value of the component (B) are SP value {component (A)}> SP value {component (B)}.

[3] The SP value of component (A) is 14.5 ≦ SP value {component (A)} ≦ 20.0, and the SP value of component (B) is 9.0 ≦ SP value {component (B) } ≦ 16.0 The curable composition according to [1] or [2].

[4] The content of the component (B) is 25.0 to 99.5% by weight based on the total amount of the component (A) and the component (B), according to any one of [1] to [3] The curable composition as described.

[5] The curable composition according to any one of [1] to [4], wherein the (meth) acrylic polymer is a resin having a hydrogen bonding group and a (meth) acryloyl group.

[6] The curable composition according to [5], wherein the hydrogen bonding group is a hydroxyl group.

[7] The curable composition according to any one of [1] to [6], further comprising the following component (C).
Component (C): inorganic particles having an average primary particle size of 1 μm or less

[8] The content of component (C) is 0.05 to 30 parts by weight with respect to a total of 100 parts by weight of component (A), component (B), and component (C). Curable composition.

[9] The curable composition according to any one of [1] to [8], wherein the (meth) acrylic polymer is obtained by a ring-opening / addition reaction of a compound having an oxirane structure.

[10] A cured product obtained by curing the curable composition according to any one of [1] to [9].

[11] A laminate obtained by forming on a substrate a hard coat layer obtained by curing the curable composition according to any one of [1] to [9].

[12] A hard coat film obtained by curing the curable composition according to any one of [1] to [9].

[13] A film laminate obtained by laminating the hard coat film according to [12] with another resin film.

  According to the present invention, there is provided a curable resin composition that is excellent in antiblocking property when formed into a cured product, can form fine irregularities on the surface after application, and can control the height of the irregularities. can do. Moreover, according to this invention, when it is set as hardened | cured material, the curable resin composition excellent in the slip property of the surface after application | coating can be provided.

  Hereinafter, embodiments of the present invention will be described in detail. However, the following descriptions are representative examples of embodiments of the present invention, and the present invention is not limited to these contents, and various modifications can be made within the scope of the gist of the present invention. It can be implemented with deformation.

  In the present invention, “to” means that numerical values described before and after are included as a lower limit value and an upper limit value. In the present invention, “polymerization” is a broad sense polymerization including so-called “copolymerization” unless otherwise specified. Therefore, in the present invention, “polymer” includes “copolymer”. Further, in the present invention, “room temperature” refers to the temperature of the place where the experiment or the like is performed, for example, a temperature of 15 to 30 ° C., more preferably 20 to 25 ° C. In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate, and means either one or both. The same applies to “(meth) acrylic acid”, “(meth) acryloyl group” and the like.

<Curable composition>
The curable composition which is one embodiment of the present invention (hereinafter sometimes abbreviated as “the curable composition of the present invention”) includes the following component (A) and component (B).
Component (A): (meth) acrylic polymer having a weight average molecular weight (Mw) exceeding 5,000 Component (B): dendrimer (meth) acrylate having a weight average molecular weight (Mw) of 5,000 or less

  The present inventors use a curable composition containing the component (A) and the component (B) to form fine irregularities on the surface after coating, and to further control the height of the irregularities. It was found to be a composition. Although the reason why the curable composition of the present invention can control the height of the unevenness is not sufficiently clear, the (meth) acrylic polymer of component (A) and the dendrimer (meta) of component (B) ) When acrylate is mixed, phase separation occurs in the curable composition, and fine irregularities can be formed on the surface after coating. In particular, component (B) is a dendrimer (meth) acrylate. Thus, for example, it is considered that this phase separation is promoted and the unevenness formed is higher than when polyfunctional (meth) acrylate other than dendrimer (meth) acrylate such as dipentaerythritol hexaacrylate is used. .

  The SP value is an abbreviation for solubility parameter (solubility parameter) and is a measure of solubility. The larger the SP value, the higher the polarity. Conversely, the smaller the value, the lower the polarity.

In the present invention, the SP value can be obtained by the following method. Weigh 0.5 g of sample into a 100 mL Erlenmeyer flask and add 10 mL of propylene glycol monomethyl ether to dissolve the resin. While stirring with a magnetic stirrer, hexane is dropped, and the dripping amount (vh) of hexane at the point where the solution becomes cloudy (turbid point) is determined. Next, when deionized water is used instead of hexane, the dripping amount (vd) of deionized water at the cloud point is obtained. From vh and vd, the SP value is given in References: SUH, CLARKE, J. P. S. A-1, 5, 1671-1681 (1967). Further, when the solubility parameter cannot be obtained by the above method, for example, the sample does not dissolve in propylene glycol monomethyl ether, the method proposed by Fedors et al. (Hereinafter sometimes referred to as “fadeers method”). It can be calculated. Specifically, it can be obtained by referring to “POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147 to 154)”.

  In the curable composition of the present invention, the SP value of the component (A) (SP value {component (A)}) and the SP value of the component (B) (SP value {component (B)}) are SP values { The relationship of component (A)}> SP value {component (B)} is preferable because phase separation between component (A) and component (B) is promoted.

  The specific value of SP value {component (A)} is not particularly limited, but preferably SP value {component (A)} ≧ 14.5, more preferably SP value {component (A)} ≧ 15.5. More preferably, the SP value {component (A)} ≧ 16.5, and the SP value {component (A)} ≦ 22.0 or less, more preferably 20.0 or less. When the SP value {component (A)} is not less than the above lower limit value, it tends to easily form fine irregularities on the surface after coating, and when it is not more than the above upper limit value, the curable composition is transparent. From the viewpoint of sex. In addition, when the curable composition of this invention contains 2 or more types of (meth) acrylic-type polymer, SP value {component (A)} is each of the (meth) acrylic-type polymer of component (A). The SP value is obtained and calculated as a weight average value of these values.

  The specific value of the SP value of component (B) (SP value {component (B)}) is not particularly limited, but preferably SP value {component (B)} ≦ 16.0, more preferably SP. Value {component (B)} ≦ 15.5, more preferably SP value {component (B)} ≦ 15.0, while preferably SP value {component (B)} ≧ 9.0. More preferably, the SP value {component (B)} ≧ 9.5, still more preferably the SP value {component (B)} ≧ 10.0, and particularly preferably the SP value {component (B)} ≧ 10. .5. If the SP value {component (B)} is not less than the above lower limit value, it is preferable from the viewpoint of transparency of the curable composition, and if it is not more than the above upper limit value, fine irregularities are formed on the surface after coating. This is preferable because it tends to be easy. In addition, when the curable composition of this invention contains 2 or more types of dendrimer (meth) acrylate, SP value {component (B)} calculates | requires each SP value of the dendrimer (meth) acrylate of a component (B). The weight average value of these values shall be calculated.

(Ingredient (A))
The curable composition of this invention contains the (meth) acrylic-type polymer of a component (A). In the present invention, “(meth) acrylic polymer” means a polymer synthesized from a raw material containing (meth) acrylic acid and / or a (meth) acrylic acid derivative, and this polymer is further modified. It is used in the meaning including polymer. The polymer is not particularly limited as long as it is a polymer using at least one raw material ((meth) acrylate monomer) among (meth) acrylic acid or (meth) acrylic acid derivatives (for example, other than (meth) acrylate monomer) The copolymer may be a copolymer using a known polymerizable monomer such as a hydrocarbon monomer having a vinyl group, etc. The “(meth) acrylic acid derivative” is a metal salt of (meth) acrylic acid. , (Meth) acrylic acid esters, (meth) acrylic acid amides and the like are meant to mean compounds having a structure similar to (meth) acrylic acid).

The weight average molecular weight (Mw) of the (meth) acrylic polymer is 5,000 or more, preferably 7,000 or more, more preferably 9,000 or more, and usually 100,000 or less, preferably Is 70,000 or less, more preferably 50,000 or less, and still more preferably 30.000 or less. When the weight average molecular weight (Mw) of the (meth) acrylic polymer is within the above range, it becomes easy to form fine irregularities on the surface after coating. In addition,
The weight average molecular weight (Mw) of the (meth) acrylic polymer can be determined as a conversion value based on polystyrene standards using gel permeation chromatography (GPC).

Preferred examples of the (meth) acrylic polymer include a polymer having at least a structure derived from the compound represented by the following formula (1).
_{CH 2 = C (-R) -C} (= O) -O-R '(1)

  In formula (1), R represents a hydrogen atom or a methyl group, and R ′ may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a halogen atom. An organic group having 1 to 24 carbon atoms is represented. Note that “may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a halogen atom” means an organic group composed only of carbon atoms and hydrogen atoms. Not only an organic group in which a part of the carbon skeleton is substituted with these atoms, and a hydroxyl group, amino group, thiol group, carboxyl group, ester group, sulfonyl group, amide group, phosphorous containing these atoms. It means that an organic group having a functional group such as an acid ester group, an ether group, or a glycidyl group is included.

  The (meth) acrylic polymer of component (A) is preferably a polymer having two or more types of structures as the structure represented by formula (1). When it has two or more types of structures, it is easy to control the SP value, for example, and a structure necessary for obtaining desired physical properties such as a structure having an effect of increasing hardness can be introduced. It becomes easy to adjust physical properties, such as the hard-coat layer formed from the curable composition of this invention, and this curable composition.

  Examples of the structure contained in the (meth) acrylic polymer include the following structures (1-1) and (1-2).

(1-1) Structure in which R ′ is an organic group having 1 to 24 carbon atoms having a hydrogen bonding group in formula (1) In formula (1), R ′ has 1 to 24 carbon atoms having a hydrogen bonding group The structure which is an organic group (hereinafter sometimes abbreviated as “(1-1) structure”) has an effect of increasing the SP value of the (meth) acrylic polymer, for example, a (meth) acrylic polymer. The SP value of the (meth) acrylic polymer of component (A) can be adjusted by the constitutional ratio of the structure (1-1) and the number of organic hydrogen-bonding groups. The number of hydrogen bonding groups in the organic group is preferably 1 or more, preferably 4 or less, more preferably 2 or less. The carbon number of the organic group is preferably 1 or more, more preferably 3 or more, preferably 22 or less, more preferably 18 or less. The hydrogen bonding group means a functional group capable of forming a hydrogen bond with other functional groups, specifically a hydroxyl group, an amino group, a thiol group, a carboxyl group, an ester group, a sulfonyl group, an amide group, Examples thereof include a phosphate ester group, an ether group, and a glycidyl group, and a hydroxyl group, an amino group, an amide group, a carboxyl group, and a glycidyl group are preferable.

(1-2) Structure in which R ′ is a C1-C24 organic group having a carbon-carbon unsaturated bond in Formula (1) R ′ is the number of carbons having a carbon-carbon unsaturated bond in Formula (1) The structure of 1 to 24 organic groups (hereinafter sometimes abbreviated as “(1-2) structure”) has an effect of increasing the hardness of the hard coat layer to be formed, for example, (meth) acrylic The hardness of the hard coat layer and the like to be formed can be adjusted by the composition ratio of the structure (1-2) in the polymer. The number of carbon-carbon unsaturated bonds in the organic group is usually 1. The carbon number of the organic group is preferably 1 or more, more preferably 3 or more, preferably 22 or less, more preferably 18 or less. The carbon-carbon unsaturated bond means a carbon-carbon double bond or a carbon-carbon triple bond, preferably a carbon-carbon double bond, and the carbon-carbon double bond is (meta More preferably, it is an acryloyl group.

  The (meth) acrylic polymer preferably has the structure (1-1), and more preferably has the structures (1-1) and (1-2). Furthermore, the (meth) acrylic polymer of component (A) includes (meth) acrylate monomers other than these structures and (meth) acrylamide in addition to the structures of (1-1) and (1-2). A monomer or the like may be copolymerized.

  The raw materials used for producing the (meth) acrylic polymer and the preparation method thereof are not particularly limited, and known methods can be appropriately selected.

For example, as raw materials to be used, in addition to acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) acrylate, phenoxyethyl (meth) acrylate, ethoxyethyl (meth) ) Alkyl such as acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. (Meth) acrylate monomers;
Glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) (Meth) acrylate monomers having an oxirane structure such as acrylate;
(Meth) acrylate monomers having a fluoroalkyl group such as perfluorohexylethyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate;
(Meth) acrylate monomers having an amino group such as N, N-diethylaminoethyl (meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate;
(Meth) acrylate monomers having a hydroxyl group such as 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate;
Moreover, as raw materials other than (meth) acrylic acid derivatives, styrene, p-chlorostyrene, p-methoxystyrene, divinylbenzene, N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, ethylene glycol divinyl ether, pentaerythritol divinyl ether, Vinyl groups such as 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified bisphenol A divinyl ether, pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, ditrimethylolpropane polyvinyl ether And hydrocarbon-based monomers having
In addition, the raw material to be used is not limited to one type, and two or more types may be used in combination to prepare a (meth) acrylic polymer, or two or more types may be used in combination to prepare a (meth) acrylic polymer. It is preferable.

  Among these, it is preferable to use a (meth) acrylate monomer having an oxirane structure, and it is more preferable to use glycidyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate. When a (meth) acrylate monomer having an oxirane structure is used, the obtained polymer is easily modified, and various structures can be easily introduced into the (meth) acrylic polymer. As described later, for example, the structure of (1-1) and the structure of (1-2) can easily form the introduced oxirane structure.

  The polymerization conditions for producing the (meth) acrylic polymer are not particularly limited, and a known method can be appropriately selected. Usually, the reaction to obtain a (meth) acrylic polymer is a radical polymerization reaction, and a (meth) acrylic polymer can be obtained by polymerizing raw material monomers in the presence of a radical polymerization initiator in an organic solvent. it can.

  For example, organic solvents include ketone solvents such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ethylene glycol dimethyl ether, propylene glycol monomethyl ether Ether solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, ester solvents such as 2-ethoxyethyl acetate, and aromatic hydrocarbon solvents such as toluene. These organic solvents may be used alone or in combination of two or more.

  Radical polymerization initiators include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide, 2,2′-azobisbutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) And azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more.

  The polymerization temperature is usually 20 to 150 ° C, preferably 50 to 100 ° C. The polymerization time is usually 1 to 72 hours, preferably 3 to 36 hours.

  As described above, when a (meth) acrylate monomer having an oxirane structure is used as a raw material for the component (A) (meth) acrylic polymer, the obtained polymer is easily modified. A method for forming the structure of (1-1) and the structure of (1-2) from a polymer obtained using a monomer will be described.

For example, when a polymer obtained by using glycidyl methacrylate as a (meth) acrylate monomer having an oxirane structure is reacted with a hydroxycarboxylic acid such as lactic acid, for example, as represented by the following formula (2): 1-1) can be formed (having two hydroxyl groups as hydrogen bonding groups).

Further, for example, when a polymer obtained by using glycidyl methacrylate as a (meth) acrylate monomer having an oxirane structure is reacted with a carboxylic acid having a (meth) acryloyl group such as acrylic acid, the following formula (3) As represented by (1-2), the structure of (1-2) can also be formed.

  The (meth) acrylic polymer of component (A) used in the present invention preferably has a secondary hydroxyl group equivalent (introduced amount of secondary hydroxyl group) of 1.0 mmol / g or more from the viewpoint of improving antiblocking properties. 2.0 mmol / g or more is more preferable, and 3.0 mmol / g or more is particularly preferable. In addition, from the viewpoint of compatibility with the component (B) dendrimer (meth) acrylate, the secondary hydroxyl group equivalent is preferably 10.0 mmol / g or less, more preferably 8.0 mmol / g or less, It is particularly preferably 6.0 mmol / g or less. The secondary hydroxyl group equivalent is calculated based on the raw material to be used, and it is preferable to react the raw material monomer by appropriately combining the above formulas (2) and (3) so that the secondary hydroxyl group equivalent falls within the above range. .

  The (meth) acrylic polymer of component (A) used in the present invention has a (meth) acryloyl equivalent (introduced amount of (meth) acryloyl group) of 1 from the viewpoint of improving scratch resistance of the cured product to be formed. It is preferably 0 mmol / g or more, more preferably 2.0 mmol / g or more, and particularly preferably 3.0 mmol / g or more. From the viewpoint of preventing gelation, the (meth) acryloyl equivalent is preferably 10.0 mmol / g or less, more preferably 8.0 mmol / g or less, and 6.0 mmol / g or less. Particularly preferred. The (meth) acryloyl equivalent is calculated based on the raw material to be used, and it is preferable to select the reaction such as the formula (3) so that the (meth) acryloyl equivalent is in the above range.

  The reaction between the oxirane structure of the polymer and the carboxylic acid (hydroxycarboxylic acid and / or carboxylic acid) can be used to form two or more types of structures. For example, the oxirane structure of the polymer is first reacted with a hydroxycarboxylic acid to form the structure (1-1), and then the remaining oxirane structure is reacted with a carboxylic acid having a carbon-carbon unsaturated bond to give (1- The structure of 2) can also be formed.

  The reaction conditions for the oxirane structure of the polymer as shown in the above formulas (2) and (3) and the carboxylic acids are not particularly limited, and a known method can be appropriately selected.

  The reaction may be either non-catalyzed or in the presence of a catalyst. Examples of the catalyst include tertiary amines such as triethylamine and benzyldimethylamine, ammonium salts such as tetraethylammonium chloride and tetrabutylammonium bromide, triphenylphosphine, and tributyl. Examples thereof include phosphines such as phosphine, and phosphonium salts such as tetrabutylphosphonium bromide and tetrabutylphosphonium iodide. The amount of the catalyst used is usually 0.5% by weight or more, preferably 1.0% by weight or more, usually 5.0% by weight or less, preferably 3.5% by weight, based on the weight of the polymer. It is as follows.

  The reaction temperature is usually 20 to 200 ° C, preferably 50 to 150 ° C. Moreover, reaction time is 1 to 72 hours normally, Preferably it is 3 to 20 hours.

  The (meth) acrylic polymer preferably uses the method of the above reaction (2) as a method for forming the structure of (1-1), that is, the (meth) acrylic polymer has an oxirane structure. A polymer obtained by reacting a (meth) acrylic polymer with a hydroxycarboxylic acid is preferable because the SP value of the component (A) is higher and the antiblocking property tends to be improved. .

  The hydroxycarboxylic acid should be appropriately selected according to the target (meth) acrylic polymer. For example, the carbon number is usually 2 or more, preferably 3 or more, and usually 10 or less, preferably Is 9 or less. Further, the number of —OH groups is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 6 or less, more preferably 2 or less. Specific examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, glyceric acid, dimethylolpropionic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, and γ-hydroxybutyric acid. Among these, lactic acid is particularly preferable from the viewpoint of reactivity with the oxirane structure, reaction control, and the like.

  The ratio (weight ratio) of the (meth) acrylic polymer having an oxirane structure and the hydroxycarboxylic acid used when the (meth) acrylic polymer having an oxirane structure is reacted with the hydroxycarboxylic acid is preferably 95. 0: 5.0 to 50.0: 50.0, more preferably 93.0: 7.0 to 60.0: 40.0, and still more preferably 90.0: 10.0 to 70.0: 30. 0.

  The (meth) acrylic polymer preferably uses the method of the above reaction (3) as a method of forming the structure of (1-2), that is, the (meth) acrylic polymer has an oxirane structure. The polymer is preferably a polymer obtained by reacting a (meth) acrylic polymer having a carboxylic acid having a carbon-carbon unsaturated bond.

  The carboxylic acid having a (meth) acryloyl group such as acrylic acid should be appropriately selected according to the target (meth) acrylic polymer. For example, the carbon number is usually 2 or more, preferably 3 These are usually 10 or less, preferably 9 or less. Specifically, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, pentaerythritol tri (meth) acrylate and succinic anhydride, phthalic anhydride And adducts of acid anhydrides such as hexahydrophthalic anhydride, adducts of acid anhydrides such as dipentaerythritol penta (meth) acrylate and succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and the like. Among these, acrylic acid is particularly preferable.

  A (meth) acrylic polymer having an oxirane structure and a carbon-carbon unsaturated bond used when a (meth) acrylic polymer having an oxirane structure is reacted with a carboxylic acid having a carbon-carbon unsaturated bond The ratio (weight ratio) of the carboxylic acid is preferably 95.0: 5.0 to 50.0: 50.0, more preferably 93.0: 7.0 to 60.0: 40.0, still more preferably It is 90.0: 10.0-70.0: 30.0.

  The (meth) acrylic polymer of component (A) contained in the curable composition of the present invention is not limited to one type, and two or more types may be included.

  The content of component (A) in the curable composition of the present invention (total content in the case of two or more types) should be appropriately selected according to the use of the curable composition, but component (A) And usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, and usually 20% by weight or less, preferably 15% by weight or less, more preferably based on the total amount of component (B). 10% by weight or less.

  The content of component (A) in the curable composition of the present invention (the total content in the case of two or more types) is appropriately selected according to the use of the curable composition, but component (A) and component ( The total amount of B) is preferably 0.5% by weight or more, more preferably 1.5% by weight or more, still more preferably 2.5% by weight or more, and preferably 75.0% by weight or less, More preferably, it is 65.0 weight% or less, More preferably, it is 55.0 weight% or less.

(Ingredient (B))
The curable composition of this invention contains the dendrimer (meth) acrylate whose weight average molecular weight (Mw) of a component (B) is 5,000 or less. In the present invention, “dendrimer (meth) acrylate” means a polyfunctional (meth) acrylate having a structure in which a branched structure is further branched to form a multi-branched structure, and the branched structure is radially expanded (the present invention). "Polyfunctional (meth) acrylate" means a compound having a plurality of (meth) acryloyl groups), and is usually used in a concept including what is called "hyperbranched polymer". .

The production method of the dendrimer (meth) acrylate of component (B) is not particularly limited. For example, a multiple branched structure is formed by repeating the reaction represented by the following formula (4), and the following formula (5) By reacting with the core compound to form a dendrimer structure as in the reaction represented by the following, the structure of the branch of the dendrimer is reacted with (meth) acrylic acid and / or a (meth) acrylic acid derivative. Can be manufactured.

  In addition to the above production method, the production method of the dendrimer (meth) acrylate of component (B) can also be obtained by the following production method.

First, a hydroxy acid having at least two hydroxyl groups is successively reacted with an alcohol to obtain a compound having a multi-branched structure and having a plurality of hydroxyl groups at the terminals. The reaction time in this sequential reaction is usually 3 to 60 hours, preferably 5 to 40 hours, and the reaction temperature is usually 50 to 200 ° C, preferably 60 to 150 ° C. In addition, this reaction can be normally implemented in presence of an acid catalyst in an organic solvent.

  The alcohol that can be used in the above method is not particularly limited, and examples thereof include methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, and dipentaerythritol. These alcohols may be used alone or in combination of two or more, but it is preferable to use one alcohol from the viewpoint of obtaining a dendrimer (meth) acrylate having a regular structure.

  The hydroxy acid having two or more hydroxyl groups is not particularly limited, and examples thereof include dimethylolpropionic acid, glyceric acid, mevalonic acid, and pantoic acid. These hydroxy acids may be used alone or in combination of two or more, but it is preferable to use one hydroxy acid from the viewpoint of obtaining a regular dendrimer (meth) acrylate.

  Furthermore, the organic solvent that can be used in this reaction is not particularly limited, and examples thereof include cyclohexane, n-hexane, heptane, methylcyclohexane, toluene and the like. The acid catalyst is not particularly limited, and examples thereof include organic acids such as p-toluenesulfonic acid, methanesulfonic acid, and benzenesulfonic acid; inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and boric acid.

  As a method for controlling the above reaction more strictly, as disclosed in JP-A-2008-81725, a hydroxyl group of a compound having a multi-branched structure and having a plurality of hydroxyl groups at the terminal is converted to benzylidene. The method of protecting by etc. is mentioned. In order to deprotect this method for the next step, a method of washing with an acid such as hydrochloric acid can be mentioned.

  A compound having a multi-branched structure obtained by the above reaction and having a plurality of hydroxyl groups at the terminal is reacted with a (meth) acrylate having a functional group capable of reacting with a hydroxyl group, and a plurality of terminals are reacted. By introducing a (meth) acryloyl group, a dendrimer (meth) acrylate can be obtained. In this reaction, the reaction time is usually 1 to 12 hours, preferably 3 to 8 hours, and the reaction temperature is usually 50 to 200 ° C, preferably 60 to 150 ° C. In addition, this reaction can be implemented in presence of the same acid catalyst in the organic solvent similar to the sequential reaction in a previous process.

  Examples of this possible functional group that reacts with a hydroxyl group include a carboxyl group, an epoxy group, and an isocyanate group. In addition, the (meth) acrylate having a functional group capable of reacting with a hydroxyl group is not particularly limited. For example, a carboxyl group such as a succinic acid adduct of (meth) acrylic acid or pentaerythritol tri (meth) acrylate (Meth) acrylate having an epoxy group such as glycidyl (meth) acrylate; (meth) acrylate having an isocyanate group such as isocyanate ethyl (meth) acrylate. These may be used alone or in combination of two or more.

  Specific dendrimer (meth) acrylates include, for example, V # 1000, SIRIUS-501 and SUBARU-501 manufactured by Osaka Organic Chemical Industry Co., Ltd. Among the dendrimer (meth) acrylates of component (B), examples of the hyperbranched polymer include SARTOMER (registered trademark) CN2302, CN2303, CN2304 and the like manufactured by Sakai Kogyo Co., Ltd.

  The dendrimer (meth) acrylate of the component (B) contained in the curable composition of the present invention is not limited to one type, and two or more types may be contained.

  The weight average molecular weight (Mw) of the dendrimer (meth) acrylate of a component (B) is 5,000 or less. When the weight average molecular weight (Mw) of the curable composition is 5,000 or less, the distance between crosslinking points when cured is in an appropriate range, and the hardness after curing can be improved. Further, from the viewpoint of making this curing better, the weight average molecular weight (Mw) is preferably 4,000 or less, more preferably 3,000 or less. On the other hand, the lower limit is usually 300 or more, preferably 500 or more.

  Dendrimer (meth) acrylates usually tend to have lower viscosities when the weight average molecular weight is comparable to polyfunctional (meth) acrylates other than dendrimer (meth) acrylates. In the curable composition of the present invention, the component (B) dendrimer (meth) acrylate has a viscosity at 25 ° C. of preferably 100 mPa · s or more, more preferably 200 mPa · s or more, and preferably 1, 500 mPa · s or less, more preferably 1,000 mPa · s or less. The viscosity at 25 ° C. can be measured with an E-type viscometer.

  In the present invention, the (meth) acrylic polymer of component (A) and the dendrimer (meth) acrylate of component (B) preferably have functional groups that react with each other. By having such a functional group, the resistance of the formed hard coat layer and the like can be increased. Such functional group combinations include active hydrogen-containing functional groups (hydroxyl groups, amino groups, thiol groups, carboxyl groups, etc.) and epoxy groups, active hydrogen-containing functional groups and isocyanate groups, ethylenically unsaturated groups and ethylene. An unsaturated group (polymerization of an ethylenically unsaturated group occurs), a silanol group and a silanol group (condensation polymerization of a silanol group occurs), a silanol group and an epoxy group, a functional group having active hydrogen and an active hydrogen Functional groups, active methylene and acryloyl groups, oxazoline groups and carboxyl groups and the like can be mentioned. The "functional group that reacts with each other" means that the reaction does not proceed only with the (meth) acrylic polymer of component (A) and the dendrimer (meth) acrylate of component (B), but a polymerization initiator is added. In some cases, the reaction proceeds.

  The content of component (B) in the curable composition of the present invention (in the case of two or more types, the total content) is appropriately selected according to the use of the curable composition, but component (A) and component ( The total amount of B) is preferably 25.0% by weight or more, more preferably 35.0% by weight or more, still more preferably 45.0% by weight or more, and preferably 99.5% by weight or less, More preferably, it is 98.5 weight% or less, More preferably, it is 97.5 weight% or less.

(Multifunctional (meth) acrylate)
In addition to the component (A) and the component (b), the curable composition of the present invention includes a polyfunctional (meth) acrylate (however, the “polyfunctional (meth) acrylate” herein includes the component (A) and the component ( The height of the unevenness to be formed can be adjusted by including B). The curable composition of this invention can contain polyfunctional (meth) acrylates other than a component (A) and a component (B) as polyfunctional (meth) acrylate. The height of the unevenness | corrugation formed can be adjusted because the curable composition of this invention contains a component (A), a component (B), and polyfunctional (meth) acrylate.

The polyfunctional (meth) acrylate does not correspond to the component (A) and the component (B) and is not particularly limited as long as it has two or more (meth) acryloyl groups, but the number of (meth) acryloyl groups is: Preferably it is 3 or more. Further, the polyfunctional (meth) acrylate also preferably has a functional group that reacts with the component (A) and the component (B). Such functional groups are the same as those mentioned in the description of the dendrimer (meth) acrylate of component (B).

  The molecular weight (weight average molecular weight (Mw)) of the polyfunctional (meth) acrylate is usually 100 or more, preferably 200 or more, more preferably 300 or more, and usually 8,000 or less, preferably 6,000. Below, more preferably 4,000 or less. When it is within the above range, the distance between cross-linking points is set to an appropriate range, and a coating film having sufficient hardness can be obtained.

  As polyfunctional (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) Examples include acrylate, tripropylene glycol di (meth) acrylate, nanoethylene glycol di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, neopentyl glycol di (meth) acrylate, and dipentaerythritol hexaacrylate. The polyfunctional (meth) acrylate preferably does not contain an ethylene oxide (EO) structure. When such a polyfunctional (meth) acrylate is used, it is easy to ensure the hardness of the hard coat layer to be formed. Moreover, polyfunctional (meth) acrylate which can be contained in the curable composition of this invention is not restricted to one type, Two or more types may be contained.

  The specific value of the SP value of the polyfunctional (meth) acrylate (SP value {polyfunctional (meth) acrylate}) is not particularly limited, but preferably the SP value {polyfunctional (meth) acrylate} ≦ 16.0. Yes, more preferably SP value {polyfunctional (meth) acrylate} ≦ 15.5, still more preferably SP value {polyfunctional (meth) acrylate} ≦ 15.0, while preferably SP value {multifunctional Functional (meth) acrylate} ≧ 9.0, more preferably SP value {polyfunctional (meth) acrylate} ≧ 9.5, and still more preferably SP value {polyfunctional (meth) acrylate} ≧ 10.0. Particularly preferably, the SP value {polyfunctional (meth) acrylate} ≧ 10.5. If the SP value {polyfunctional (meth) acrylate} is not less than the above lower limit value, it is preferable from the viewpoint of the transparency of the curable composition, and if it is not more than the above upper limit value, fine irregularities are formed on the surface after coating. It is preferable because it tends to be formed easily. In addition, when the curable composition of this invention contains 2 or more types of dendrimer (meth) acrylate, SP value {polyfunctional (meth) acrylate} calculates | requires each SP value of polyfunctional (meth) acrylate, and these It shall be calculated as a weight average value of the values.

  When polyfunctional (meth) acrylate is used for the curable composition of the present invention, the content thereof is preferably 5% by weight based on the total amount of component (A), component (B) and polyfunctional (meth) acrylate. More preferably 10% by weight or more, on the other hand, preferably 90% by weight or less, more preferably 70% by weight or less, still more preferably 50% by weight or less, particularly preferably 30% by weight. % Or less. In the said range, the unevenness | corrugation of the desired hardened | cured material surface can be controlled by using polyfunctional (meth) acrylates other than a component (A) and a component (B).

(Ingredient (C))
It is preferable that the curable composition of the present invention further contains the following component (C) from the viewpoint of further improving the antiblocking property and making the cured product high in hardness.
Component (C): inorganic particles having an average primary particle size of 1 μm or less

Inorganic particles of component (C) include silica (including organosilica sol), alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (Indium oxide / tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, antimony oxide and the like. In addition, the inorganic particles are not limited to one type, and two or more types may be included.

The average primary particle diameter of the inorganic particles of the component (C) is usually 1 μm or less, preferably 500 nm or less, more preferably 200 nm or less, further preferably 100 nm or less, while usually 5 nm or more, preferably Is 10 nm or more. Within this range, thermal diffusion dominates rather than sedimentation due to gravity, making it possible to disperse particles stably in the composition, and to effectively have inorganic particles on the surface when a hard coat layer is formed. Can be made. Moreover, there exists a tendency for an optical characteristic to become favorable, so that the average primary particle diameter of an inorganic particle is small. In addition, the average primary particle diameter of the inorganic particle in this invention calculates | requires the specific surface area measured value (based on JISZ8830) by a BET adsorption method, and is a value calculated | required as a conversion value from the following formula | equation.
[Average primary particle diameter (nm)] = 6,000 / [[specific surface area (m ² / g)] × [density (g / cm ³ )]]

  The content of component (C) in the curable composition of the present invention (the total content in the case of two or more types) is 100 parts by weight in total of component (A), component (B) and component (C). Preferably it is 0.05 parts by weight or more, more preferably 0.5 parts by weight or more, even more preferably 0.7 parts by weight or more, particularly preferably 1 part by weight or more, while preferably 30 parts by weight or less, more preferably Is 20 parts by weight or less, more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less.

(Polymerization initiator)
If the curable composition of this invention contains a component (A) and a component (B), although it does not specifically limit about another component, Usually, a polymerization initiator is included.

  The polymerization initiator is not particularly limited as long as it can accelerate the curing reaction between the component (A) and the component (B), and a known one can be appropriately selected. For example, alkylphenone type compounds (α-hydroxyacetophenone type, α-aminoacetophenone type, benzyl ketal type, etc.), acylphosphine oxide type compounds, oxime ester compounds, oxyphenyl acetates, benzoin ethers, phenyl formates And ketone / amine compounds. Specifically, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2, 4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Photopolymerization initiators such as butan-1-one, methylbenzoylformate, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone It is. The polymerization initiator may be used alone or in combination of two or more.

  The content of the polymerization initiator in the curable composition of the present invention (total content in the case of two or more types) is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight. These are usually 20% by weight or less, preferably 10% by weight or less.

(Silicone oil)
The curable composition of the present invention contains a (meth) acryloyl polymer of component (A) and a dendrimer (meth) acrylate of component (B), whereby a (meth) acryloyl polymer and dipentaerythritol hexa Compared with a polyfunctional (meth) acrylate other than a dendrimer (meth) acrylate such as an acrylate, a cured product having a larger surface roughness (Ra) described later can be obtained. By further containing silicone oil in the curable composition, the cured product having a larger surface roughness (Ra) can have a reduced coefficient of friction in combination with the concavo-convex structure, thereby improving the slipperiness of the cured product surface. It is preferable because it can be improved.

  It does not restrict | limit especially as a silicone oil which can be included in the curable composition of this invention, A well-known thing can be used. Specifically, silicone oil is composed of a linear polymer composed of siloxane bonds. As a linear polymer comprising a siloxane bond, a part of the side chain is a methyl group, a part of the side chain and both ends or one end is a methyl group, and a part of the side chain is a phenyl group And those in which a part of the side chain is a hydrogen bonding group and those in which a part of the side chain is a hydrogen atom. Among these, all of the side chains and both ends or one end are methyl groups, some of the side chains are hydrogen-bonding groups, and some of the side chains are hydrogen atoms. From the viewpoint of good blocking properties and good optical properties, those having all side chains and both ends or one end being methyl groups are particularly preferred from the viewpoint of surface segregation. Silicone oil can introduce various organic groups, and the properties differ depending on the type of organic group. Examples of the organic group that can be introduced into the silicone oil include an alkyl group, an aralkyl group, a hydroxyl group, an acryloyl group, a carboxyl group, a carbonyl group, a fluoro group, an amino group, and an epoxy group. Among these, since an antiblocking property is favorable, an alkyl group, an aralkyl group, a hydroxyl group, an acryloyl group, a carboxyl group, a carbonyl group and an epoxy group are preferable, and an alkyl group, an aralkyl group, a hydroxyl group and an acryloyl group are particularly preferable. These silicone oils can be obtained as commercial products. For example, the corresponding product can be selected from the BYK series manufactured by BYK Chemie, the Silface series manufactured by Nissin Chemical Industry, and the like.

  The silicone oils listed above may be used alone or in combination of two or more. Further, when the curable composition of the present invention contains silicone oil, the content thereof is preferably 0.001 part by weight or more with respect to 100 parts by weight in total of the component (A) and the component (B), It is more preferably 0.05 parts by weight or more, further preferably 0.1 parts by weight or more, and on the other hand, it is preferably 20 parts by weight or less, more preferably 10 parts by weight or less. The amount is more preferably 0.0 parts by weight or less, and particularly preferably 3.0 parts by weight or less. When the content of the silicone oil is within the above range, it is preferable from the viewpoint of the slipperiness and antiblocking property of the cured product surface.

(solvent)
The curable composition of the present invention preferably contains a solvent in order to be used as a hard coat layer of a PET film.

  Solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether. , Ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; dimethylformamide, diethylformamide, N-methyl Amido solvents such as pyrrolidone; methyl cellosolve, ethyl cellosolve, Cellosolve solvents such as Ruserosorubu; methanol, ethanol, propanol, isopropanol, alcohol solvents butanol; dichloromethane, halogenated solvents such as chloroform and the like. In addition, a solvent is not restricted to one type, Two or more types may be contained.

  There is no restriction | limiting in particular in the usage-amount of a solvent, Considering the applicability | paintability of the curable composition prepared, the viscosity of a liquid, compatibility of solid content, etc., it determines suitably. The curable composition of the present invention is usually prepared as a coating solution having a solid content of 20 to 99.9%, particularly 30 to 80% by weight, using the above-mentioned solvent. Here, the “solid content” in the curable composition of the present invention means the total of components excluding the solvent contained in the curable composition of the present invention.

(Other optional ingredients)
The curable composition of the present invention may contain additives such as a surface conditioner, an antioxidant, and an ultraviolet absorber, and the type and content thereof are not particularly limited. The content of these additives is usually 0.01% by weight or more, preferably 0.05% by weight or more, respectively, relative to 100 parts by weight of the total of component (A) and component (B). The amount is usually 10% by weight or less, preferably 5% by weight or less, and more preferably 2% by weight or less.

  For example, as the surface conditioner, Polyflow No. manufactured by Kyoeisha Chemical Co., Ltd. 75, Polyflow No. 77 and other polymer leveling agents. The surface conditioner may be used alone or in combination of two or more.

  Examples of the antioxidant include hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like. Only one type of antioxidant may be used, or two or more types may be used in combination.

  Examples of the UV absorber include benzotriazole UV absorbers, benzophenone UV absorbers, salicylic acid UV absorbers, cyanoacrylate UV absorbers, and triazine UV absorbers. Only one type of ultraviolet absorber may be used, or two or more types may be used in combination.

(Method for preparing curable composition)
The method for preparing the curable composition of the present invention is not particularly limited. For example, the component (A), the component (B) and, if necessary, the polyfunctional (meth) acrylate, the component (C), the silicone oil, the polymerization initiator. It can be prepared by mixing a solvent, an additive and the like. As described above, when inorganic particles are used, the inorganic particles are preferably used in a form that is surface-modified with the (meth) acrylic polymer of component (A).

<Hardened product / Laminate>
A cured product can be obtained by curing the curable composition of the present invention. In particular, a laminate obtained by forming a hard coat layer obtained by curing a curable composition on a substrate (hereinafter sometimes abbreviated as “laminated product of the present invention”) is also an embodiment of the present invention. is there. Moreover, a hard coat film can be obtained by curing the curable composition of the present invention. Furthermore, a film laminate can be obtained by laminating this hard coat film on another resin film as a substrate.

  In the laminate of the present invention, the type of substrate is not particularly limited as long as the hard coat layer is a layer formed by curing the curable composition of the present invention described above. Examples of the base material include various resin films and resin plates.

Examples of the resin film include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic resin film, polyurethane resin film, and polycarbonate film. , Polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth) acrylonitrile film, cycloolefin polymer (COP) film, and the like.

  Also, as the resin plate, acrylic plate, triacetyl cellulose plate, polyethylene terephthalate plate, diacetylene cellulose plate, acetate butyrate cellulose plate, polyethersulfone plate, polyurethane plate, polycarbonate plate, polysulfone plate, polyether plate, polymethyl Examples include a pentene plate, a polyether ketone plate, and a (meth) acrylonitrile plate.

  Since the curable composition of this invention is excellent in antiblocking property, it is preferable to use the resin film wound by roll shape as a base material.

  In addition, although the thickness of a base material should be suitably selected according to the use of a laminated body, it is 25-1000 micrometers normally.

  In the laminate of the present invention, the thickness of the hard coat layer is not particularly limited and can be appropriately selected depending on the use of the laminate, but is usually 0.5 μm or more, preferably 1 μm or more, more preferably 1.5 μm. These are usually 10 μm or less, preferably 7 μm or less, more preferably 5 μm or less.

  In the laminate of the present invention, the method for applying the curable composition is not particularly limited, and a known method can be appropriately selected. For example, a dip coating method, an air knife coating method, a curtain coating method, a spin coating method, a roller coating method, a bar coating method, a wire bar coating method, a gravure coating method, an extrusion coating method (US Pat. No. 2,681,294), etc. Can be mentioned.

In the laminate of the present invention, the curing method of the curable composition is not particularly limited and may be photocuring or heat curing, but is preferably photocuring. The light irradiation for curing, usually integrated light quantity irradiated 100 mJ / cm ² or more 20,000mJ / cm ² or less and so as. As the light source, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal, a ride, a xenon flash, an ultraviolet LED, an electron beam, or the like can be used.

  The laminate of the present invention has excellent antiblocking properties by forming fine irregularities on the surface of the hard coat layer, but it is preferable that the surface roughness (Ra) of the hard coat layer surface is large. For example, when the hard coat layer is formed with a thickness of 2 μm, the surface roughness (Ra) is preferably 20 nm or more, preferably 30 nm or more, more preferably 40 nm or more. The upper limit is not particularly limited, but is usually 100 nm or less. In addition, surface roughness (Ra) means arithmetic mean roughness (Ra), and can be measured with a high-intensity non-contact three-dimensional surface shape roughness meter (WYKO NT9100 manufactured by VEECO).

The total light transmittance and haze when the curable composition of the present invention is applied onto a substrate and the film thickness after drying of the layer made of the curable composition is 2 μm, the total light transmittance is usually 85. % Or more, preferably 90% or more, and haze is usually 2.0% or less, preferably 1.8% or less, more preferably 1.5% or less, and further preferably less than 1.0%. The total light transmittance can be measured using, for example, a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.), and the total light transmittance (Tt (%)) is incident light on the hard coat layer. It is a value calculated from the following equation by measuring the intensity (T ₀ ) and the total transmitted light intensity (T ₁ ) transmitted through the hard coat layer.
Tt (%) = (T ₁ / T ₀ ) × 100

Haze can be measured using, for example, a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7136. The haze can be calculated from the following formula.
H (%) = (Td / Tt) × 100
(H: Haze (cloudiness value) (%), Td: Diffuse light transmittance (%), Tt: Total light transmittance (%)

  The curable composition of the present invention can be suitably used for various applications by adopting the form of the above-described cured product and laminate. Specifically, the curable composition of the present invention includes a liquid crystal display device (liquid crystal display), an LED (light emitting diode display), an ELD (electroluminescence display), a VFD (fluorescent display), a PDP (plasma display panel), and the like. It can be used as a flat panel display. Particularly suitable for touch panel films that operate devices by holding down the display on the screen, such as bank ATMs, vending machines, personal digital assistants (PDAs), copiers, facsimiles, game machines, museums, department stores, etc. It is useful for guidance display devices, car navigation systems, multimedia stations (multifunctional terminals installed in convenience stores), mobile phones, railway vehicle monitoring devices, etc.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. That is, materials, usage amounts, ratios, processing contents, processing procedures, and the like can be appropriately changed without departing from the spirit of the present invention.

<Evaluation method>
In the following examples and comparative examples, various evaluations were performed by the following methods.

(Anti-blocking property)
Are two laminates prepared, and after the cured film surfaces are superposed at 23 ° C. and a relative humidity of 60% and a load of about 1 kg is applied by finger pressure, are the cured film surfaces have slipperiness? The anti-blocking property was evaluated according to the following criteria.
◎: Can be easily slid ○: Can be slid, no sound is produced △: Can be slid but sound is produced ×: The cured film surfaces are in close contact with each other Things that cannot be slid

(Surface roughness (Ra))
The obtained laminate was allowed to stand in a temperature-controlled room at 23 ° C. and a relative humidity of 60% for 12 hours, and then the surface roughness (Ra) of the hard coat layer was determined as a high-intensity non-contact three-dimensional surface shape roughness meter (WYKO manufactured by VEECO). NT9100).

<Synthesis Example 1: Synthesis of (meth) acrylic polymers A and B>
(1) In a reaction vessel, 157.3 g of propylene glycol monomethyl ether, 98.0 g of glycidyl methacrylate (GMA), 1.0 g of methyl methacrylate (MMA), 1.0 g of ethyl acrylate (EA), 1.9 g of mercaptopropyltrimethoxysilane, Then, 1.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted at 65 ° C. for 3 hours. Thereafter, 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours, and then 138.1 g of propylene glycol monomethyl ether and 0.45 g of p-methoxyphenol were added and 100 ° C. Until heated. Next, 50.7 g of acrylic acid and 3.1 g of triphenylphosphine were added and reacted at 110 ° C. for 6 hours to obtain a (meth) acrylic polymer having an acryloyl group and a methoxysilyl group (solid content: 30% by weight). Hereinafter, the obtained (meth) acrylic polymer is referred to as (meth) acrylic polymer A.

(2) The (meth) acrylic polymer A had an acryloyl group equivalent (acryloyl group introduction amount) of 4.47 mmol / g, a secondary hydroxyl group equivalent (secondary hydroxyl group introduction amount) of 4.47 mmol / g. These values are values calculated based on the weight of the raw material used.

(3) The weight average molecular weight (Mw) of the (meth) acrylic polymer A was 20,000. This value is a value measured by the GPC method under the following conditions.
Equipment: “HLC-8120GPC” manufactured by Tosoh Corporation
Column: “TSKgel Super H1000 + H2000 + H3000” manufactured by Tosoh Corporation
Detector: Differential refractive index detector (RI detector / internal)
Solvent: Tetrahydrofuran Temperature: 40 ° C
Flow rate: 0.5 mL / min Injection volume: 10 μL
Concentration: 0.2% by weight
Calibration sample: Monodisperse polystyrene calibration method: Polystyrene conversion

(4) The SP value of the (meth) acrylic polymer A was 17.8. This SP value is a value measured by a method based on the turbidity method shown below.
At a measurement temperature of 20 ° C., 0.5 g of (meth) acrylic polymer A was weighed into a 100 mL beaker, 10 g of a good solvent (propylene glycol monomethyl ether) was added, and dissolved while stirring with a magnetic stirrer. Next, a low SP poor solvent (n-hexane) was gradually added dropwise to the diluted solution using a 50 mL dropping funnel, and the point at which the polymer solution became cloudy was defined as the amount of the low SP poor solvent added. Separately, a high SP poor solvent (ion exchange water) was gradually added dropwise to the diluted solution, and the point at which the polymer solution became turbid was defined as the amount of the high SP poor solvent added. The SP value of the (meth) acrylic polymer A was calculated from the amount of dripping up to the cloud point of each poor solvent.

(5) In a reaction vessel, 3.75 parts by weight of (meth) acrylic polymer A and colloidal silica (manufactured by Nissan Chemical Industries, Ltd .: MEK-ST (average primary particle size 10 to 15 nm (catalog value)) 1.25 parts by weight Then, 0.005 part by weight of acetylacetone aluminum was added as a silane coupling reaction catalyst and reacted at 70 ° C. for 4 hours to prepare colloidal silica surface-modified with (meth) acrylic polymer A. (Meth) acrylic polymer B ”.

<Example 1>
(Meth) acrylic polymer B obtained in Synthesis Example 1, V # 1000 (dendrimer acrylate, SP value: 14.3, weight average molecular weight (Mw): 1,900 (SP value) The weight average molecular weight (Mw) is a value obtained by the same method as that for the (meth) acrylic polymer A))), Kyoeisha Chemical Co., Ltd. Polyflow No. 77 (Polymer-based surface conditioner, SP value: 10.3 (calculated value by the Fedodors method (catalog value))) and BASF Irgacure (registered trademark) 184 (abbreviated as “Irg184” in Table 1, polymerization) Initiator)) ((meth) acrylic polymer B: V # 1000: Polyflow No. 77: Irgacure (registered trademark) 184 = 5.0: 95.0: 1.0: 2.5 (solid content) ), And further diluted with a propylene glycol-methyl ethyl ketone mixed solvent (PG: MEK = 7: 3 (volume ratio)) to obtain a curable composition. In Table 1, (meth) acrylic polymer B is a mixture of (meth) acrylic polymer A and MEK-ST, and the total of (meth) acrylic polymer A and V # 1000 is based on 100 parts by weight. In terms of conversion, the formulation of the curable composition is shown.

The obtained curable composition was coated on a biaxially stretched PET film (trade name: Diafoil (registered trademark) O321E, 125 μm, manufactured by Mitsubishi Plastics) so that the film thickness after drying with a bar coater was 2 μm. , And dried at 80 ° C. for 1 minute. After drying, it was cured by UV irradiation (conditions: 500 mJ / cm ² , 450 mW / cm ² ) to form a hard coat layer to obtain a laminate. About this laminated body, evaluation of antiblocking property and the measurement of surface roughness (Ra) were performed by the said method. The results are shown in Table 1.

<Comparative Example 1>
Dipentaerythritol hexaacrylate (abbreviated as “DPHA” in Table 1, SP value: 12.1, weight average molecular weight (Mw): 730 (SP value and weight average) The molecular weight (Mw) is a value obtained by the same method as that for the (meth) acrylic polymer A))), and a curable composition was obtained in the same manner as in Example 1. Further, a hard coat layer was formed in the same manner as in Example 1 to obtain a laminate. About this laminated body, like Example 1, evaluation of antiblocking property and the measurement of surface roughness (Ra) were performed.

<Evaluation results>
As can be seen from Table 1, Example 1 and Comparative Example 1 are both excellent in anti-blocking properties, but Example 1 provides a laminate having a surface roughness (Ra) greater than that of Comparative Example 1. It was.

  Cured products obtained by curing the curable composition of the present invention include liquid crystal display devices (liquid crystal displays), LEDs (light emitting diode displays), ELDs (electroluminescent displays), VFDs (fluorescent displays), and PDPs (plasma displays). It can be used as a flat panel display such as a panel. Particularly suitable for touch panel films that operate devices by holding down the display on the screen, such as bank ATMs, vending machines, personal digital assistants (PDAs), copiers, facsimiles, game machines, museums, department stores, etc. It is useful for guidance display devices, car navigation systems, multimedia stations (multifunctional terminals installed in convenience stores), mobile phones, railway vehicle monitoring devices, etc.

Claims (13)

A curable composition comprising the following component (A) and the following component (B).
Component (A): (meth) acrylic polymer having a weight average molecular weight (Mw) exceeding 5,000 Component (B): dendrimer (meth) acrylate having a weight average molecular weight (Mw) of 5,000 or less   The curable composition of Claim 1 whose SP value of a component (A) and SP value of a component (B) are SP value {component (A)}> SP value {component (B)}.   The SP value of the component (A) is 14.5 ≦ SP value {component (A)} ≦ 20.0, and the SP value of the component (B) is 9.0 ≦ SP value {component (B)} ≦ 16 The curable composition according to claim 1, which is 0.0.   Hardening of any one of Claims 1-3 whose content of a component (B) is 25.0-99.5 weight% with respect to the total amount of a component (A) and a component (B). Sex composition.   The curable composition according to any one of claims 1 to 4, wherein the (meth) acrylic polymer is a resin having a hydrogen bonding group and a (meth) acryloyl group.   The curable composition according to claim 5, wherein the hydrogen bonding group is a hydroxyl group. Furthermore, the curable composition of any one of Claims 1-6 containing the following component (C).
Component (C): inorganic particles having an average primary particle size of 1 μm or less   The curable composition of Claim 7 whose content of a component (C) is 0.05-30 weight part with respect to a total of 100 weight part of a component (A), a component (B), and a component (C). object.   The curable composition according to any one of claims 1 to 8, wherein the (meth) acrylic polymer is obtained by a ring-opening / addition reaction of a compound having an oxirane structure.   Hardened | cured material formed by hardening | curing the curable composition of any one of Claims 1-9.   The laminated body formed by forming the hard-coat layer formed by hardening | curing the curable composition of any one of Claims 1-9 on a base material.   A hard coat film obtained by curing the curable composition according to claim 1.   The film laminated body formed by laminating | stacking the hard coat film of Claim 12 with another resin film.