JP5603622B2 - Radical polymerizable composition, coating material, hard coat agent, and composite - Google Patents

Description

  The present invention relates to a radically polymerizable composition, a coating material, a hard coating agent, and a composite. More specifically, for example, the visibility of fingerprint stains adhering to the surface of a molded article such as a film or sheet made of wood, paper, glass, plastic, etc., that is, the attached fingerprints are difficult to see and have excellent wiping properties, and scratches. The present invention relates to a radically polymerizable composition, a coating material, a hard coating agent, and a composite excellent in transparency that can form a film capable of preventing the generation of the above.

Touch panels, CDs, DVDs, Blu-rays used in displays, ATMs, ticket vending machines, POS terminals, handy terminals, FA devices, copiers, etc. used in televisions, small game machines, mobile phones, car navigation systems, personal computers, digital cameras, etc. Surface layer part of magnetic recording media such as discs, HD-DVDs, surface coating parts such as roofs of buildings, outer walls and waterproofing layers, bathtubs, bathrooms, wash bowls, mirrors, kitchen sinks, toilet bowls and other surface layers, cameras The surface layers of plastic lenses such as video cameras and glasses are required to have excellent antifouling properties and scratch resistance (abrasion resistance), and the surface layers are usually provided with antifouling properties. For this purpose, a hard coat layer is often provided.
In particular, in recent years, a touch panel type device that directly operates with a finger is directly used on a display screen of a liquid crystal or EL display device. There is a need for a hard coat agent that can form a hard coat layer that is difficult to adhere.
As a method for preventing contamination due to fingerprints, for example, a hard coat agent containing a fluorine resin additive is known (see Patent Documents 1 and 2).
The hard coat layer formed using the hard coat agent was still prominently contaminated with fingerprint-derived stains, but had the advantage that the stains could be easily removed by wiping. However, it is not sufficient in terms of the ease of wiping, and stains left after wiping spread on the surface of the hard coat layer, and the stains may become more noticeable.
As a method for improving the fingerprint adhesion preventing effect and the ease of wiping off when a fingerprint is adhered, for example, a method of introducing a silicon-based skeleton such as polysiloxane into a resin has been studied (see Patent Document 3). ).
According to the method, although the wiping property of the fingerprint can be improved, the stain derived from the fingerprint is still conspicuous.
Patent Document 4 discloses a urethane resin-containing fingerprint-resistant photocurable composition having a polyether skeleton.
However, the fingerprint wiping property and the visibility on the surface of the coating formed using the fingerprint-resistant photocurable composition are still not practically sufficient.
In this way, dirt derived from fingerprints is not noticeable (fingerprint visibility), and even if fingerprints are attached, they must be easily removable by wiping off (fingerprint wiping properties). Actually, no coating material capable of forming a compatible film has yet been found.

Japanese Patent Laid-Open No. 10-104403 JP 2004-250474 A Japanese Patent Laid-Open No. 10-7986 JP 2008-255301 A

  The problem to be solved by the present invention is, for example, excellent in both visibility and wiping of fingerprint stains attached to the surface of a molded article such as a film or sheet made of wood, paper, glass, plastic, etc. Free-radically polymerizable composition capable of forming a film capable of preventing oxidization, a coating material using the radical polymerizable composition, a hard coating agent using the radical polymerizable composition, and the coating material or hard It is to provide a composite having a coating formed using a coating agent.

The radical polymerization composition according to claim 1 of the present invention comprises a urethane (meth) acrylate (A) having an alkyl group derived from an alkyl polyether compound (a) as a terminal, and a terminal derived from the alkyl polyether compound (a). Polyfunctional (meth) having three or more polymerizable unsaturated double bonds as the polymerizable unsaturated monomer (C) and urethane (meth) acrylate (B) having no alkyl group and polyether skeleton A radical polymerizable composition containing an acrylic compound , wherein the urethane (meth) acrylate (A) has a functional group of the alkyl polyether compound (a) and one or more polymerizable unsaturated double bonds. a polymerizable monomer and the functional group of (c) is state, and are not bound via a compound having two isocyanate groups (b), the urethane (meth) acrylate The mass ratio of the content of the urethane (meth) acrylate (A) to the content of (B) is in the range of [(A) / (B)] = 5/95 to 70/30, and the radical polymerizable property Content of the said polyfunctional (meth) acrylic-type compound with respect to the mass of a composition is 50-70 mass%, It is characterized by the above-mentioned.
The radical polymerization composition according to claim 2 of the present invention is characterized in that, in claim 1, the HLB value calculated by the Griffin formula or Davis method of the alkyl polyether compound (a) is less than 3 to 13. And
The radical polymerization composition according to claim 3 of the present invention is the radical polymerization composition according to claim 1, wherein the alkyl polyether compound (a) comprises an alkyl group at one end, a polyether skeleton as a main chain, and the other It is a compound comprised from the hydroxyl group of the terminal of this.
The radical polymerization composition according to claim 4 of the present invention is the radical polymerization composition according to any one of claims 1 to 3, wherein the alkyl polyether compound (a) is represented by the following general formulas (1) and (2). It is any one selected from the following compounds.
_{-O- C n H m (CH (} R) CH 2 -O) X -H ... (1)
_{C n H m -C (= O} ) O- (CH (R) CH 2 -O) X -H ... (2)
[In the formula, n represents an integer of 8 to 20, m represents an integer of 2n-5 to 2n + 1 , R represents H, —CH ₃ , —CH ₂ —CH ₃ , and X represents 2 to 50] Represents an integer. ]
The radical polymerization composition according to claim 5 of the present invention is the radical polymerization composition according to claim 4, wherein n in the general formulas (1) and (2) is an integer of 8 to 20, and m is 2n-5 to 2n + 1. It is an integer and X is an integer of 2-20.
The radical polymerization composition according to claim 6 of the present invention is the radical polymerization composition according to any one of claims 1 to 5 , wherein the urethane (meth) acrylate (A) comprises an alkyl polyether compound (a), a hydroxyl group, and 2 It is a reaction product of a polymerizable monomer (c) having at least one polymerizable unsaturated double bond and an alicyclic or aliphatic compound (b) having two isocyanate groups. And
The radical polymerization composition according to claim 7 of the present invention is the radical polymerization composition according to any one of claims 1 to 6 , wherein the urethane (meth) acrylate (B) has an alicyclic or aliphatic isocyanate group. It is a reaction product of a compound (b) having two and a polymerizable monomer (c) having a hydroxyl group and two or more polymerizable unsaturated double bonds.
A covering material according to an eighth aspect of the present invention is characterized by comprising the radical polymerizable composition according to any one of the first to seventh aspects.
The hard coat agent according to claim 9 of the present invention is characterized by comprising the radically polymerizable composition according to any one of claims 1 to 7 .
Composite according to claim 1 0 of the present invention, the substrate surface, and having a coating film formed using the hard coat agent of the dressing or claim 9, wherein according to claim 8.

According to the radically polymerizable composition of the present invention, it is possible to form a high-hardness film excellent in visibility and wiping property of attached fingerprints, and in transparency and scratch resistance, among antifouling properties.
In addition, the radical polymerizable composition of the present invention is used for active energy curing, room temperature curing using a combination of a peroxide and a reducing agent, heat curing using a peroxide, and curing by any curing method. The hardening method according to can be employ | adopted.
According to the coating material using the radically polymerizable composition of the present invention, a high-hardness film having excellent visibility and wiping property of attached fingerprints, transparency and scratch resistance can be obtained.
According to the hard coat agent using the radically polymerizable composition of the present invention, a highly hard coating (hard coat layer) excellent in the visibility and wiping off of the attached fingerprint, transparency, and scratch resistance can be obtained.
Composites having a film formed using the coating material or hard coat agent of the present invention (for example, displays and ATMs used in televisions, small game machines, mobile phones, car navigation systems, personal computers, digital cameras, etc., ticket machines, Touch panel used for POS terminal, handy terminal, FA equipment, copier, etc. Surface layer of magnetic recording media such as CD, DVD, Blu-ray disc, HD-DVD, roof of buildings, exterior walls, waterproof layers, etc. , Surface layers of bathtubs, bathrooms, wash bowls, mirrors, kitchen sinks, toilet bowls, etc., surface layers of plastic lenses such as cameras, camcorders, glasses, etc.) With the use of the composite, because it is excellent in visibility and wiping of attached fingerprints, transparency, and scratch resistance Flip ur it is possible to prevent spoiling the appearance of the surface layer portion.

  The radical polymerizable composition of the present invention comprises a urethane (meth) acrylate (A) having an alkyl group derived from an alkyl polyether compound (a) at the terminal, a terminal alkyl group derived from the alkyl polyether compound (a) and a poly It is a radically polymerizable composition containing a urethane (meth) acrylate (B) having no ether skeleton and a polymerizable unsaturated monomer (C).

  The urethane (meth) acrylate (A) used in the present invention is a functional group of an alkyl polyether compound (a) and a functional group of a polymerizable monomer (c) having one or more polymerizable unsaturated double bonds. And a group bonded through a compound (b) having two isocyanate groups.

  The urethane (meth) acrylate (A) is an alkyl polyether compound for forming a high-hardness film having excellent fingerprint visibility (fingerprint adhesion prevention), fingerprint wiping property, transparency, and scratch resistance. It is essential to have a terminal alkyl group derived from (a).

  In addition, as the urethane (meth) acrylate (A), it is possible to use a film having one or more (meth) acryloyl groups that can contribute to the formation of a cured film, resulting in a film having high hardness and excellent scratch resistance. It is preferable in forming, and it is more preferable to use one having 2 to 6. Therefore, the polymerizable monomer (c) having an unsaturated double bond is preferably a monomer composed of a (meth) acrylic compound ((meth) acrylic acid derivative). Detailed specific examples will be described later.

  The urethane (meth) acrylate (A) includes an alkyl polyether compound (a) having a hydroxyl group, a polymerizable monomer (c) having a hydroxyl group and one or more polymerizable unsaturated double bonds, and an isocyanate group. As a reaction product with a compound (b) having two

  Specifically, the urethane (meth) acrylate (A) is obtained by reacting, for example, a hydroxyl group of an alkyl polyether compound and a compound (b) having two isocyanate groups, the alkyl polyether compound (a ) Derived structure (terminal alkyl group and polyether skeleton) and an isocyanate group compound (d), and a polymerizable monomer (c) having a hydroxyl group and one or more polymerizable unsaturated double bonds. It can be produced by reacting.

More specifically, for example, the hydroxyl group of the alkyl polyether compound (a) and the compound (b) having two isocyanate groups are reacted so that the equivalent ratio (isocyanate group / hydroxyl group) is 2 to 100. It is preferable to make it. Here, the equivalent ratio (isocyanate group / hydroxyl group) is the equivalent of the isocyanate group (NCO) of the compound (b) having two isocyanate groups and the equivalent of the hydroxyl group of the alkyl polyether compound (a). Equivalent ratio.
The said compound (d) which has a urethane bond by the said reaction is obtained, and then the polymerizable monomer (c) which has the isocyanate group which the said compound (d) has, a hydroxyl group, and one or more polymerizable unsaturated double bonds ) And further forming a urethane bond to produce the urethane (meth) acrylate (A) or a mixture of the urethane (meth) acrylate (A) and the urethane (meth) acrylate (B). be able to.

Next, the alkyl polyether compound (a) will be described.
As the alkyl polyether compound (a), it is important to use a compound having a polyalkylene oxide chain composed of a ring-opening reaction product of an alkylene oxide and having an alkyl group at the terminal.
By controlling the polarity of the coating surface and improving familiarity with the lipids that are the components of fingerprints, fingerprint visibility and fingerprint wiping will be improved, and the HLB value calculated by the Griffin or Davis method will be controlled. This is very important.

The HLB value calculated from the Griffin or Davis method of the alkyl polyether compound (a) is preferably 3 to less than 13.
By using the alkyl polyether compound (a) having an HLB value of 3 to less than 13, the fingerprint visibility and the fingerprint wiping property are remarkably improved.

  The HLB value (HLB) here is a value representing the degree of affinity of the surfactant for water and oil (an organic compound insoluble in water). HLB is an acronym for Hydrophile-Lipophile Balance. This concept was proposed in 1949 by William Griffin of Atlas Powder Company. The HLB value takes a value from 0 to 20, and the closer to 0, the higher the lipophilicity and the closer to 20, the higher the hydrophilicity. Several methods for determining by calculation have been proposed. The Griffin method is defined as HLB value = 20 × sum of formula weight of hydrophilic part / molecular weight, and Davis method determines the number of groups determined by functional groups (for example, methyl group). And a methylene chain is defined as a lipophilic group 0.475, a hydroxyl group is a hydrophilic group 1.9, etc.), HLB value = 7 + total number of hydrophilic groups−total number of lipophilic groups.

  The radically polymerizable composition of the present invention contains the urethane (meth) acrylate (A) having an alkyl group derived from the alkyl polyether compound (a) at the terminal, thereby using the radically polymerizable composition of the present invention. The fingerprint visibility and fingerprint wiping property of the coating formed can be improved, and the effect of relieving the stress generated when the coating cured product is cured can also be obtained.

  The alkyl polyether compound (a) is preferably a compound composed of an alkyl group at one end, a polyether skeleton as a main chain, and a hydroxyl group at the other end.

Examples of the polyether skeleton (polyether chain) include polyalkylene oxides such as polyethylene oxide, polypropylene oxide, and polybutylene oxide. Polyethylene oxide is preferable.
As said polyalkylene oxide, 2-50 mol addition product of alkylene oxide is preferable, and 2-20 mol addition product is more preferable.

  The alkyl group (alkyl chain) is not particularly limited, and examples thereof include 2-ethylhexyl, oleyl, tridecyl, castor oil, cetyl, stearyl and the like. The alkyl group is preferably an alkyl group having 1 to 50 carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms.

  The alkyl polyether compound (a) needs to have an active hydrogen atom-containing group that reacts with the isocyanate group of the compound (b) having two isocyanate groups described later. Here, the active hydrogen atom-containing group is preferably a hydroxyl group. The hydroxyl group is preferably present at the terminal of the alkyl polyether compound (a).

  As said alkyl polyether compound (a), it is preferable to use the thing of 50-5000 hydroxyl equivalent, and it is more preferable to use the thing of 200-2000.

Examples of the alkyl polyether compound (a) include any one compound selected from the following general formulas (1) and (2).
_{-O- C n H m (CH (} R) CH 2 -O) X -H ... (1)
_{C n H m -C (= O} ) O- (CH (R) CH 2 -O) X -H ... (2)
Wherein, n, m represents an integer of 1 to 50, R represents _{H, -CH 3, -CH 2 -CH} 3, a, X represents an integer of 2 to 50. ]
In the general formulas (1) and (2), it is preferable that n is an integer of 8 to 20, m is an integer of 2n-5 to 2n + 1, and X is an integer of 2 to 20. It is preferable that n, m, and X are values in the above range because the coating film has excellent balance of fingerprint visibility, fingerprint wiping property, transparency, and scratch resistance.

  Examples of commercially available products of the alkyl polyether compound (a) include New Coal 1203, 1204, 1305, 1525, 1606, etc., manufactured by Nippon Emulsifier Co., Ltd., and NOF Corporation, Nonion E202, E205, S202, Examples include, but are not limited to, K204, O2, S2, and L2.

Next, the compound (b) having two isocyanate groups used for the production of the urethane (meth) acrylate (A) will be described.
The compound (b) having two isocyanate groups refers to a compound having two isocyanate groups in the molecule, such as hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, 2 3,4-tolylene diisocyanate, its isomers or a mixture of these isomers, 4,4-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), xylylene diisocyanate, norbornene diisocyanate and other diisocyanates, and the diisocyanate and trimethylolpropane, etc. An adduct with an aliphatic polyhydric alcohol of a valence or higher, an isocyanurate structure which is a trimer of diisocyanate, a burette formed by reaction of diisocyanate and water, Details, it is also possible to use a polymeric MDI and the like.

As the compound (b) having two isocyanate groups, from the viewpoint of preventing discoloration of the cured product of the radical polymerizable composition of the present invention, an alicyclic or aliphatic compound having two isocyanate groups is used. It is preferable to use two isocyanate groups containing a cyclohexane ring, a norbornene ring, and a nurate skeleton from the viewpoint of improving the surface hardness and heat resistance of the resulting coating and improving the compatibility of the composition of the present invention. It is more preferable to use the compound (b) which has.
Here, “aliphatic” means having no aromatic hydrocarbon group, and means having a linear or branched alkyl group or alkylene group. The “alicyclic system” means having a cyclic aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic.

Next, a polymerizable monomer (c) having a polymerizable unsaturated double bond used for the production of the urethane (meth) acrylate (A) (hereinafter simply referred to as “polymerizable unsaturated double bond-containing monomer”). (C) may be described. "
The number of the polymerizable double bond which the polymerizable unsaturated double bond containing monomer (c) in this invention has should just be one or more.
The polymerizable unsaturated double bond-containing monomer (c) is an essential component for increasing the hardness of the film and imparting the effect of improving scratch resistance.
As the polymerizable unsaturated double bond-containing monomer (c), only a polymerizable monomer having one polymerizable unsaturated double bond such as a generally known 2-hydroxyethyl (meth) acrylate is used. Although it may be used, in order to improve the scratch resistance effect, it is desirable to use a polymerizable monomer ((meth) acrylic compound) having two or more polymerizable unsaturated double bonds.

The polymerizable unsaturated double bond of the polymerizable unsaturated double bond-containing monomer (c) is preferably in the range of 2 to 6.
The polymerizable unsaturated double bond-containing monomer (c) preferably has a hydroxyl group capable of reacting with the isocyanate group of the compound (b) having two isocyanate groups to form a urethane bond. .

  The urethane (meth) acrylate (A) in the present invention includes an alkyl polyether compound (a), a polymerizable monomer (c) having a hydroxyl group and two or more polymerizable unsaturated double bonds, and an alicyclic type. Alternatively, it is preferably a reaction product with an aliphatic compound (b) having two isocyanate groups.

Examples of the polymerizable unsaturated double bond-containing monomer (c) include trimethylolpropane di (meth) acrylate, trimethylolpropane methacrylate methacrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol tetra (meth). Polymerization having hydroxyl group and two or more polymerizable unsaturated double bonds such as acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate A monomer (c-1) can be used individually or in combination of 2 or more types.
Among these, the use of trimethylolpropane di (meth) acrylate, trimethylolpropane methacrylate (acrylate), pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, etc. It is preferable for further improving and imparting excellent scratch resistance.

  When producing the urethane (meth) acrylate (A) used in the present invention, the polymerizable unsaturated double bond-containing monomer (c) is a hydroxyl group and two or more polymerizable unsaturated double bonds. In addition to the polymerizable monomer (c-1) having a polymerizable group, a polymerizable monomer (c-2) having a hydroxyl group and one polymerizable unsaturated double bond may be used in combination.

  Examples of the polymerizable unsaturated double bond-containing monomer (c-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. [Epsilon] -caprolactone adduct and the like can be used.

  In the radically polymerizable composition of the present invention, the polymerizable unsaturated double bond-containing monomer (c-1) and the polymerizable unsaturated double bond-containing monomer (c-2) are used in combination. The amount of the polymerizable unsaturated double bond-containing monomer (c-2) used is less than the amount of the polymerizable unsaturated double bond-containing monomer (c-1) used. It is preferable to use it.

  In addition, when producing the urethane (meth) acrylate (A) used in the present invention, the polymerizable unsaturated double bond is used for the purpose of preventing curing inhibition by air of the radical polymerizable unsaturated composition of the present invention. In addition to the containing monomer (c), a hydroxyl group-containing allyl ether compound may be used.

  Examples of the hydroxyl group-containing allyl ether compound include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, and tripropylene. Glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether Glyceryl diallyl ether, pentaerythritol triallyl ether, etc. Can be used allyl ether compounds such valence alcohols, it is preferred to use the allyl ether compound having inter alia one hydroxyl group.

The urethane (meth) acrylate (A) can be produced, for example, by the following two-stage reaction process.
In the first step, the alkyl polyether compound (a) is prepared by reacting 1 equivalent of the hydroxyl group of the alkyl polyether compound (a) and 2 equivalents or more of the isocyanate group of the compound (b) having two isocyanate groups. This is a step of obtaining a compound (d) having a derived structure (terminal alkyl group and polyether skeleton) and one isocyanate group.

  This reaction step is preferably performed in a range of room temperature to about 100 ° C. in a nitrogen atmosphere. Moreover, although the said reaction process can also be performed under a non-solvent, an organic solvent and the polymerizable unsaturated monomer (C) mentioned later can also be used as a solvent as needed.

In the first stage reaction step, a catalyst may be used as necessary.
Examples of the catalyst include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; organic tin compounds such as tin octylate, dibutyltin oxide, and sibutyltin dilaurate; and further, stannous chloride, bromide Known catalysts such as acids and alkalis such as monotin and stannous iodide can be used. The amount of these catalysts added is preferably 10 to 10,000 ppm with respect to the total charge.

The second stage reaction step includes one isocyanate group of the compound (d) obtained in the first stage reaction step and the polymerizable unsaturated double bond-containing monomer (c Is a step of reacting with a hydroxyl group possessed by
The polymerizable unsaturated double bond-containing monomer (c) has a hydroxyl group 1 to 1 which the polymerizable unsaturated double bond-containing monomer (c) has per 1 equivalent of the isocyanate group of the compound (d). It is preferable to use in the range of 1.9 equivalents.

  This reaction step is preferably performed in a range of room temperature to about 90 ° C. in a nitrogen atmosphere. Moreover, although the said reaction process can also be performed under a non-solvent, an organic solvent and the polymerizable unsaturated monomer (C) mentioned later can also be used as a solvent as needed.

In the second-stage reaction step, the same catalyst as exemplified as being usable in the first-stage reaction step may be used as necessary.
Moreover, in order to suppress the radical polymerization of the polymerizable unsaturated double bond of the polymerizable unsaturated double bond-containing monomer (c), a radical polymerization inhibitor can be used as necessary.

  As the radical polymerization inhibitor, for example, hydroquinone monomethyl ether, dt-butyl hydroquinone, pt-butyl catechol, phenothiazine and the like can be used. The amount of the radical polymerization inhibitor used is preferably 10 to 10,000 ppm with respect to the total charge.

The content of the urethane (meth) acrylate (A) is preferably in the range of 1 to 90% by mass, and in the range of 1 to 50% by mass, based on the total amount of the radical polymerizable composition of the present invention. It is more preferable. Moreover, the mass ratio of the content of the urethane (meth) acrylate (A) to the content of the urethane (meth) acrylate (B) described later is [(A) / (B)] = 1/99 to 99/1. Is preferable, and the range of 5/95 to 70/30 is more preferable.
By being in the above-mentioned range, it is possible to form a high-hardness film that is further excellent in contamination removal (fingerprint visibility and fingerprint wiping property of the film), dust adhesion prevention, and scratch resistance.

Next, urethane (meth) acrylate (B) will be described.
The urethane (meth) acrylate (B) is the same as the urethane (meth) acrylate (A) except that it does not have a structure derived from the alkyl polyether compound (a) (terminal alkyl group and polyether skeleton). It is the same, and is a reaction product of the compound (b) having two isocyanate groups and the polymerizable monomer (c) having the hydroxyl group and one or more polymerizable unsaturated double bonds. .

  Therefore, the urethane (meth) acrylate (B) does not use the alkyl polyether compound (a), the compound (b) having two isocyanate groups, the hydroxyl group and one or more polymerizable unsaturated double bonds. And a polymerizable monomer (c) having, for example, a reaction in a range of room temperature to 90 ° C. in a nitrogen atmosphere, in the absence of a solvent, in an organic solvent, or in the presence of a polymerizable unsaturated monomer (C). Can be manufactured.

  The compound (b) having two isocyanate groups and the polymerizable monomer (c) having a polymerizable unsaturated double bond used for the production of the urethane (meth) acrylate (B) include the urethane ( The thing similar to what was illustrated as what can be used for manufacture of (meth) acrylate (A) can be used.

  Moreover, as said urethane (meth) acrylate (B), what was manufactured separately from the said urethane (meth) acrylate (A) can be used, but by adjusting the preparation ratio of a raw material, the said urethane ( From the viewpoint of improving production efficiency, it is preferable to use a product that is manufactured together with the (meth) acrylate (A).

  Specifically, in the production of the urethane (meth) acrylate (A), the compound (b) having two isocyanate groups and the polymerizable non-polymerizable amount relative to the amount of the alkyl polyether compound (a) used. By using the saturated double bond-containing monomer (c) in excess, the above (A) and (B) can be produced collectively.

  The content of the urethane (meth) acrylate (B) is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, based on the total amount of the radical polymerizable composition of the present invention. . When it is in the above range, a film having high hardness and further excellent scratch resistance can be formed.

  The urethane (meth) acrylate (B) comprises an alicyclic or aliphatic compound (b) having two isocyanate groups, a polymerizable single group having a hydroxyl group and two or more polymerizable unsaturated double bonds. A reaction product of the monomer (c) is preferable.

Next, the polymerizable unsaturated monomer (C) will be described.
Examples of the polymerizable unsaturated monomer (C) include styrene, vinyl toluene, methyl styrene, paramethyl styrene, chloro styrene, dichloro styrene, divinyl benzene, vinyl naphthalene, divinyl naphthalene, ethyl vinyl ether, methyl vinyl ether, methyl. (Meth) acrylate, ethyl (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate or its ε-caprolactone adduct, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N-vinylpyrrolidone, 1-vinylimidazole, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) Chrylate, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, 1,3-butanedi (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate Relate, dicyclopentanyl (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol di (meth) acrylate, methoxydiethylene glycol di (Meth) acrylate, methoxytriethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene Trimethylolpropane tri (meth) acrylate added with oxide, trimethylol added with propylene oxide Propane tri (meth) acrylate may be used alone or in combination of two or more kinds. In particular, the use of a polyfunctional (meth) acrylic compound having three or more polymerizable unsaturated double bonds such as pentaerythritol triacrylate improves the surface hardness of the formed film and provides excellent scratch resistance. It is preferable in giving.

  The content of the polymerizable unsaturated monomer (C) is preferably used in the range of 5 to 95% by mass with respect to the total amount of the radical polymerizable composition of the present invention.

The radically polymerizable composition of the present invention, for example, the urethane (meth) acrylate (A), the urethane (meth) acrylate (B), and the polymerizable unsaturated monomer (C) at a temperature of 60 ° C. or less. It can be manufactured by mixing and stirring all at once. When the polymerizable unsaturated monomer (C) is used as a solvent for producing the urethane (meth) acrylate (A) or the urethane (meth) acrylate (B), the polymerizable unsaturated monomer is used. The saturated monomer (C) may be previously mixed with the (A) or (B).
In addition, when the urethane (meth) acrylate (A) and the urethane (meth) acrylate (B) are produced together as described above, the mixture thereof and the polymerizable unsaturated monomer (C) are added. The radically polymerizable composition of the present invention can be produced by mixing and stirring.

  The radically polymerizable composition of the present invention can be cured by any of the curing methods of curing with active energy rays, heat curing by using a peroxide, and room temperature curing by using a peroxide and a reducing agent.

When curing with active energy rays, it is preferable to use a photopolymerization initiator as a curing agent.
Examples of the photopolymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone. And thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone and 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- Hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butano Benzophen ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2, Acylphosphine oxides such as 4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate, 1,7-bisacridinylheptane, 9-phenylacridine Etc. can be used.

  When curing by active energy rays, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate together with the photopolymerization initiator as necessary. Well-known photosensitizers such as amyl 4-dimethylaminobenzoate and 4-dimethylaminoacetophenone may be used.

  When heat-curing using a peroxide, for example, diacyl peroxide-based, peroxyester-based, hydroperoxide-based, dialkyl peroxide-based, ketone peroxide-based, peroxyketal-based, alkyl peroxide as a curing agent. Peroxides such as esters and percarbonates can be used.

  Further, when the radical polymerizable composition of the present invention is cured at room temperature, the above peroxide and a curing accelerator such as organic metal salts such as cobalt naphthenate and cobalt octenoate, dimethylaniline, diethylaniline, paratoluidine, etc. Aromatic amine compounds can be used in combination.

  The curing agent is preferably used in the range of 0.1 to 10 parts by mass, more preferably in the range of 1 to 5 parts by mass with respect to 100 parts by mass of the radical polymerizable composition of the present invention. preferable.

  Moreover, you may use a polymerization inhibitor for the radically polymerizable composition of this invention as needed. Examples of the polymerization inhibitor include trihydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, toluhydronone, p-tert-butylcatechol, 2,6-tert-butyl-4-methylphenol, and the like. . The amount of the polymerization inhibitor used is preferably 10 to 1000 ppm in the radical polymerizable composition.

The radically polymerizable composition of the present invention may contain an inorganic filler as necessary. By containing an inorganic filler, the scratch resistance and film hardness of the surface can be further improved.
Examples of the inorganic filler include metal oxide fine particles, and specific examples include silica, alumina, zirconia, and titania. These inorganic fillers more preferably have an average particle size of about 2 to 100 nm.
Moreover, in order to improve the surface smoothness of the coating film, a generally used additive such as a leveling agent may be added and used. As the additive, it is preferable to use a non-silicone or non-fluorine additive in order to maintain the effect of fingerprint visibility and fingerprint wiping property of the coating.

The radically polymerizable composition of the present invention may contain an organic solvent as a diluent solvent.
Examples of the organic solvent include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, heptane, octane, and mineral spirit; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether , Isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetole, and other ether solvents; ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol di Ester solvents such as acetate; dimethylformamide, diethylformamide Amide solvents such as dimethyl sulfoxide and N-methylpyrrolidone; cellosolv solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; ether ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; methanol, ethanol, Examples include alcohol solvents such as propanol. These solvents may be used alone or in combination.

  Examples of a method for forming a film using a coating material (hard coat agent) comprising the radically polymerizable composition of the present invention include a method in which the coating material (hard coat agent) is applied to a substrate and cured. Examples of the coating method include a spin coating method, a dip coating method, a gravure coating method, a spray method, a roller method, and a brush coating method. At this time, it is preferable to apply the coating so that the thickness of the film formed after curing is 0.1 to 30 μm. Examples of the curing method after coating include a method using the curing agent, the photopolymerization initiator, and the like.

  The radically polymerizable composition of the present invention includes generally known unsaturated polyester resins, epoxy acrylate resins, polyurethane resins, acrylic resins, alkyd resins, urea resins, melamine resins, polyvinyl acetate, Vinyl acetate copolymers, polydiene elastomers, saturated polyester resins, saturated polyethers, celluloses and derivatives thereof, fats and oils, and other conventional natural and synthetic polymer compounds are within the range not impairing the effects of the present invention. Can be used.

Since the radically polymerizable composition of the present invention is excellent in adhesion to various substrates, it can be used as a coating material for the purpose of surface protection of various substrates. Especially, the radically polymerizable composition of this invention can be used suitably as a hard-coat agent which can be used for formation of the coating film generally called a hard-coat layer which is high hardness and excellent in abrasion resistance.
Examples of the substrate include polyethylene terephthalate, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polyvinyl alcohol, hard vinyl chloride, soft vinyl chloride, ABS resin, unsaturated polyester resin, FRP made of vinyl ester resin and epoxy resin. Plastic, wood, metal, concrete, asphalt, glass, paper, etc. can be used.

  Examples of the composite having a coating formed using the coating material or the hard coating agent of the present invention include displays, ATMs, and ticket sales used in televisions, small game machines, mobile phones, car navigation systems, personal computers, digital cameras, and the like. Touch screens used in machines, POS terminals, handy terminals, factory automation equipment, copiers, etc. Surfaces of magnetic recording media such as CDs, DVDs, Blu-ray discs, HD-DVDs, roofs of buildings, exterior walls, waterproof layers, etc. Examples include painted parts, bathtubs, bathrooms, wash bowls, mirrors, kitchen sinks, toilet parts such as toilets, plastic lenses such as cameras, video cameras, and glasses. The coating formed on the surface layer of these composites is excellent in the visibility and wiping off of the attached fingerprint, transparency, and scratch resistance. Can be prevented.

  Hereinafter, the present invention will be described in more detail by way of examples.

(Synthesis Example 1)
Urethane (meth) acrylate (A-1) having an alkyl group derived from an alkyl polyether compound at the terminal, and urethane (meth) acrylate (B-) having no terminal alkyl group derived from an alkyl polyether compound and a polyether skeleton Preparation of mixture (I) with 1)

In a 1 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 22.2 parts by mass of isophorone diisocyanate, 63.3 parts by mass of methyl isobutyl ketone, and hydroquinone monomethyl ether Charge 0.1 mass part, add 17.5 mass parts of alkyl polyether compound (HLB value 6.6, New Coal 1203, Nippon Emulsifier Co., Ltd., hydroxyl value 140), 0.01 mass of tin catalyst as reaction promoting catalyst Then, the reaction was carried out at 60 ° C. for 3 hours while suppressing exotherm.
After confirming that the NCO equivalent was the theoretical value when all the hydroxyl groups of the alkyl polyether compound reacted with the isocyanate group, 213.5 parts by mass of dipentaerythritol hydroxypentaacrylate was added, and the reaction was promoted as a catalyst. 0.02 parts by mass of tin catalyst was added, and the reaction was continued in an air atmosphere at 60 ° C. for 7 hours until the NCO% became 0.3% by mass or less.
Accordingly, urethane (meth) acrylate (A-1) having an alkyl polyether compound-derived alkyl group at the terminal, and urethane (meth) acrylate having no alkyl polyether compound-terminated alkyl group and polyether skeleton. A mixture (I) with (B-1) was obtained.

(Synthesis Example 2)
Urethane (meth) acrylate (A-2) having an alkyl polyether compound-derived alkyl group at the terminal, and urethane (meth) acrylate having no terminal alkyl group and polyether skeleton derived from the alkyl polyether compound (B- Preparation of mixture (II) with 2)

In a 1 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 22.2 parts by mass of isophorone diisocyanate, 63.3 parts by mass of methyl isobutyl ketone, and hydroquinone monomethyl ether Charge 0.1 mass part, add 35.1 parts by mass of an alkyl polyether compound (New Coal 1203, manufactured by Nippon Emulsifier Co., Ltd.), add 0.01 parts by mass of tin catalyst as a reaction promoting catalyst, The reaction was carried out at 0 ° C. for 3 hours.
After confirming that the NCO equivalent was the theoretical value when all the hydroxyl groups of the alkyl polyether compound reacted with the isocyanate group, 190 parts by mass of dipentaerythritol hydroxypentaacrylate was added, and a tin catalyst was used as a reaction promoting catalyst. Was added at 60 ° C. for 7 hours under an air atmosphere until the NCO% was 0.3% by mass or less.
Accordingly, urethane (meth) acrylate (A-2) having an alkyl polyether compound-derived alkyl group at the terminal, and urethane (meth) acrylate having no alkyl group and terminal skeleton derived from the alkyl polyether compound. A mixture (II) with (B-2) was obtained.

(Synthesis Example 3)
Urethane (meth) acrylate (A-3) having an alkyl group derived from an alkyl polyether compound at the terminal, and urethane (meth) acrylate (B-) having no terminal alkyl group and polyether skeleton derived from the alkyl polyether compound Preparation of mixture (III) with 3)

In a 1 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 22.2 parts by mass of isophorone diisocyanate, 63.3 parts by mass of methyl isobutyl ketone, and hydroquinone monomethyl ether 0.1 part by mass, 17.5 parts by mass of an alkyl polyether compound (HLB value 4.9, Nonion E202, manufactured by NOF Corporation, hydroxyl value 158) were added, and 0.01 part by mass of a tin catalyst as a reaction promoting catalyst The mixture was added and reacted at 60 ° C. for 3 hours while suppressing exotherm.
After confirming that the NCO equivalent was the theoretical value when all the hydroxyl groups of the alkyl polyether compound reacted with the isocyanate group, 213.5 parts by mass of dipentaerythritol hydroxypentaacrylate was added, and the reaction was promoted as a catalyst. 0.02 parts by mass of tin catalyst was added, and the reaction was continued in an air atmosphere at 60 ° C. for 7 hours until the NCO% became 0.3% by mass or less.
Thereby, urethane (meth) acrylate (A-3) having an alkyl group derived from an alkyl polyether compound at the terminal, and urethane (meth) acrylate having no terminal alkyl group derived from an alkyl polyether compound and a polyether skeleton ( A mixture (III) with B-3) was obtained.

(Synthesis Example 4)
Urethane (meth) acrylate (A-4) having an alkyl group derived from an alkyl polyether compound at the terminal, and urethane (meth) acrylate (B-) having no terminal alkyl group and polyether skeleton derived from the alkyl polyether compound Preparation of mixture (IV) with 4)

In a 1 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 22.2 parts by mass of isophorone diisocyanate, 63.3 parts by mass of methyl isobutyl ketone, and hydroquinone monomethyl ether Charge 0.1 mass part, add 17.5 mass parts of alkyl polyether compound (HLB value 7.9, New Coal 1204, Nippon Emulsifier Co., Ltd., hydroxyl value 120), 0.01 mass of tin catalyst as reaction promoting catalyst Then, the reaction was carried out at 60 ° C. for 3 hours while suppressing exotherm.
After confirming that the NCO equivalent was the theoretical value when all the hydroxyl groups of the alkyl polyether compound reacted with the isocyanate group, 213.5 parts by mass of dipentaerythritol hydroxypentaacrylate was added, and the reaction was promoted as a catalyst. 0.02 parts by mass of tin catalyst was added, and the reaction was continued in an air atmosphere at 60 ° C. for 7 hours until the NCO% became 0.3% by mass or less.
Thereby, urethane (meth) acrylate (A-4) having an alkyl group derived from an alkyl polyether compound at the terminal, and urethane (meth) acrylate having no terminal alkyl group and polyether skeleton derived from the alkyl polyether compound ( A mixture (IV) with B-4) was obtained.

(Synthesis Example 5)
Urethane (meth) acrylate (A-5) having an alkyl group derived from an alkyl polyether compound at its terminal, and urethane (meth) acrylate (B-) having no terminal alkyl group and polyether skeleton derived from an alkyl polyether compound Preparation of mixture (V) with 5)

In a 1 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 22.2 parts by mass of isophorone diisocyanate, 63.3 parts by mass of methyl isobutyl ketone, and hydroquinone monomethyl ether Charge 0.1 mass part, add 17.5 mass parts of alkyl polyether compound (HLB value 6.6, New Coal 1203, Nippon Emulsifier Co., Ltd., hydroxyl value 140), 0.01 mass of tin catalyst as reaction promoting catalyst Then, the reaction was carried out at 60 ° C. for 3 hours while suppressing exotherm.
After confirming that the NCO equivalent was the theoretical value when all the hydroxyl groups of the alkyl polyether compound reacted with the isocyanate group, 89 parts by mass of pentaerythritol triacrylate was added, and a tin catalyst was added as a reaction promoting catalyst. 0.02 part by mass was added, and the reaction was continued at 60 ° C. for 7 hours in an air atmosphere until the NCO% became 0.3% by mass or less.
Thus, urethane (meth) acrylate (A-5) having an alkyl group derived from an alkyl polyether compound at the terminal, and urethane (meth) acrylate having no terminal alkyl group derived from an alkyl polyether compound and a polyether skeleton ( A mixture (V) with B-5) was obtained.

(Synthesis Example 6)
Urethane (meth) acrylate (A-6) having an alkyl polyether compound-derived alkyl group at the terminal, and urethane (meth) acrylate (B-) having no alkyl group and terminal skeleton derived from the alkyl polyether compound. Preparation of mixture (VI) with 6)

In a 1 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 22.2 parts by mass of isophorone diisocyanate, 63.3 parts by mass of methyl isobutyl ketone, and hydroquinone monomethyl ether Charge 0.1 mass part, add 17.5 mass parts of alkyl polyether compound (HLB value 6.6, New Coal 1203, Nippon Emulsifier Co., Ltd., hydroxyl value 140), 0.01 mass of tin catalyst as reaction promoting catalyst Then, the reaction was carried out at 60 ° C. for 3 hours while suppressing exotherm.
After confirming that the NCO equivalent was the theoretical value when all of the hydroxyl groups of the alkyl polyether compound reacted with the isocyanate group, 21 parts by mass of hydroxyethyl acrylate was added, and a tin catalyst as a reaction promoting catalyst was added in an amount of 0.001. 02 parts by mass were added, and the reaction was continued at 60 ° C. for 7 hours in an air atmosphere until the NCO% was 0.3% by mass or less.
As a result, urethane (meth) acrylate (A-6) having an alkyl group derived from an alkyl polyether compound at the terminal and urethane (meth) acrylate having no terminal alkyl group and polyether skeleton derived from an alkyl polyether compound ( A mixture (VI) with B-6) was obtained.

(Synthesis Example 7)
Urethane (meth) acrylate (A-7) having an alkyl group derived from an alkyl polyether compound at the terminal, and urethane (meth) acrylate (B-) having no terminal alkyl group and polyether skeleton derived from the alkyl polyether compound Preparation of mixture (VII) with 7)

In a 1 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 22.2 parts by mass of isophorone diisocyanate, 63.3 parts by mass of methyl isobutyl ketone, and hydroquinone monomethyl ether Charge 0.1 mass part, add 17.5 mass parts of alkyl polyether compound (HLB value 8.3, nonion O-2, NOF Corporation, hydroxyl value 125), and add 0.01 catalyst of tin catalyst as reaction promoting catalyst. Mass parts were added and reacted at 60 ° C. for 3 hours while suppressing heat generation.
After confirming that the NCO equivalent was the theoretical value when all the hydroxyl groups of the alkyl polyether compound reacted with the isocyanate group, 213.5 parts by mass of dipentaerythritol hydroxypentaacrylate was added, and the reaction was promoted as a catalyst. 0.02 parts by mass of tin catalyst was added, and the reaction was continued in an air atmosphere at 60 ° C. for 7 hours until the NCO% became 0.3% by mass or less.
Thereby, urethane (meth) acrylate (A-7) having an alkyl group derived from an alkyl polyether compound at the terminal, and urethane (meth) acrylate having no terminal alkyl group derived from the alkyl polyether compound and a polyether skeleton ( A mixture (VII) with B-7) was obtained.

(Comparative Synthesis Example 1)
Preparation of urethane (meth) acrylate (B-8) having no terminal alkyl group derived from alkyl polyether compound and polyether skeleton

In a 1 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 22.2 parts by mass of isophorone diisocyanate, 63.3 parts by mass of methyl isobutyl ketone, and hydroquinone monomethyl ether 0.1 parts by mass, 237 parts by mass of dipentaerythritol hydroxypentaacrylate, 0.17 parts by mass of tin catalyst as a reaction promoting catalyst, 7 hours at 60 ° C. in an air atmosphere, 0.3% by mass of NCO% It was made to react until it became the following.
This obtained urethane (meth) acrylate resin (B-8) which does not have a structure derived from an alkyl polyether compound.

(Comparative Synthesis Example 2)
Urethane (meth) acrylate having a polyether skeleton derived from a polyether compound and having no alkyl group at the terminal, and urethane (meth) acrylate having no alkyl group and polyether skeleton derived from the alkyl polyether compound ( Preparation of mixture (VIII) with B-9)

In a 1 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 22.2 parts by mass of isophorone diisocyanate, 63.3 parts by mass of methyl isobutyl ketone, and hydroquinone monomethyl ether Charge 0.1 parts by mass, add 20.3 parts by mass of a polyether compound (PTMG1000, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 1014), add 0.01 parts by mass of tin catalyst as a reaction promoting catalyst, and suppress heat generation. The reaction was carried out at 60 ° C. for 3 hours.
After confirming that the NCO equivalent was the theoretical value when all of the hydroxyl groups of the polyether compound reacted with isocyanate groups, 213.5 parts by mass of dipentaerythritol hydroxypentaacrylate was added, and tin as a reaction promoting catalyst was added. The catalyst was added in an amount of 0.02 parts by mass, and the reaction was carried out in an air atmosphere at 60 ° C. for 7 hours until the NCO% became 0.3% by mass or less.
As a result, urethane (meth) acrylate having a polyether skeleton derived from a polyether compound without having an alkyl polyether skeleton at the terminal, and a urethane having no terminal alkyl group and polyether skeleton derived from an alkyl polyether compound ( A mixture (VIII) with meth) acrylate (B-9) was obtained.

(Examples 1-7 and Comparative Examples 1-5)
By mixing the urethane (meth) acrylate or mixture obtained in Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 and 2 and a polymerizable unsaturated monomer according to the compositions described in Tables 1 and 2 below. The radically polymerizable compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were prepared. Further, in Comparative Example 3, Optool DAC (manufactured by Daikin Industries, Ltd.) as a fluorine-based additive as resin composition (B-8) obtained in Comparative Synthesis Example 1 is 100 parts by mass of resin composition (B-8). 2.5 parts by mass was added to the sample to prepare a sample. In Comparative Example 4, 4.5 parts by mass of BYK-SILCLEAN3700 (manufactured by Big Chemie) was added to 100 parts by mass of the resin composition (B-8) obtained in Comparative Synthesis Example 1 and used in the same manner. It was.

The fingerprint visibility, fingerprint wiping property, surface hardness, scratch resistance, and transparency of the coating were evaluated by the following methods.
(Coating method)
A coating material (hard coat agent) in which methyl ethyl ketone was added and dissolved as a solvent to each radical polymerizable composition obtained by the above method was obtained. At this time, the total solvent component contained in the hard coat agent was adjusted to 40% by mass. Thereafter, a hard coat agent obtained by adding and dissolving Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) so as to be 3% by mass in the hard coat agent was used as an optically-adhesive polyethylene terephthalate film (thickness: 100 μm) as a base material. ) (Toyobo Co., Ltd., Cosmo Shine 4100) was applied so that the thickness after curing was about 7 μm. Next, the solvent was volatilized with a dryer at 90 ° C. for 120 seconds, and the coating surface (hard coat layer) was cured by irradiating with ultraviolet rays using one UV lamp 120W metal halide (UV irradiation amount: 500 mJ / cm ² ). ) To obtain a composite comprising the coating and the substrate.

(Method for evaluating film performance)
The performance of the coating (hard coat layer) obtained above was evaluated by the following method.
Fingerprint visibility: After an actual fingerprint is attached to the surface of the film with a weight of about 1 kg, the fingerprint is observed from the front (directly above, an angle of 90 degrees with respect to the film surface) and obliquely (at an angle of 45 degrees with respect to the film surface). What was clearly visible was rated as “x”, difficult to see from the front, but clearly visible from the diagonal as “△”, and difficult to see from the front and diagonal as “◯”.

Fingerprint wiping property: After the fingerprint was attached to the coating surface in the same manner as described above, it was reciprocated three times with a load of 1 kg using tissue paper (Napier (registered trademark)). This was visually evaluated according to the following criteria.
“◯”; “△” which was able to remove almost all dirt; “X” which was able to remove about 80% or more of the dirt; about 50% of the dirt could not be removed or could not be removed White cloudiness occurred

  Surface hardness: The pencil hardness of the coating surface was measured according to JISK5400 (1 kg load). Those having a pencil hardness of 2H or more were evaluated as being excellent in surface hardness.

  Scratch resistance: The appearance of the surface of the coating was evaluated by rubbing 10 times with a load of 500 g using steel wool # 0000. “O” indicates that no scratches are observed on the surface and slight scratches are observed, “Δ” indicates that scratches are conspicuous on a part of the coating surface, and “ “×”.

  Total light transmittance, haze (HAZE): Using a haze meter (manufactured by Nippon Denshoku Co., Ltd.), the total light transmittance of the various coatings obtained above was measured, and the total light transmittance was 90% or more. “◯”, less than 90% and 85% or more are “Δ”, and less than 85% are “x”. About haze, the thing of 1.0% or less was evaluated as "(circle)", and the thing exceeding 1.0% was evaluated as "*".

Claims (10)

Urethane (meth) acrylate (A) having an alkyl group derived from an alkyl polyether compound (a) at its terminal, urethane (meth) having no terminal alkyl group derived from the alkyl polyether compound (a) and a polyether skeleton A radically polymerizable composition containing an acrylate (B) and a polyfunctional (meth) acrylic compound having three or more polymerizable unsaturated double bonds as the polymerizable unsaturated monomer (C),
The urethane (meth) acrylate (A) has a functional group of the alkyl polyether compound (a) and a functional group of a polymerizable monomer (c) having one or more polymerizable unsaturated double bonds. state, and are not bound via a compound having two isocyanate groups (b),
The mass ratio of the content of the urethane (meth) acrylate (A) to the content of the urethane (meth) acrylate (B) is in the range of [(A) / (B)] = 5/95 to 70/30. ,
Content of the said polyfunctional (meth) acrylic-type compound with respect to the mass of the said radically polymerizable composition is 50-70 mass%, The radically polymerizable composition characterized by the above-mentioned. The radically polymerizable composition according to claim 1, wherein the alkyl polyether compound (a) has an HLB value calculated by a Griffin formula or a Davis method of less than 3 to 13. The radical polymerization according to claim 1 or 2, wherein the alkyl polyether compound (a) is a compound composed of an alkyl group at one end, a polyether skeleton as a main chain, and a hydroxyl group at the other end. Sex composition. The radical polymerization property according to any one of claims 1 to 3, wherein the alkyl polyether compound (a) is any one selected from compounds represented by the following general formulas (1) and (2). Composition.
_{-O- C n H m (CH (} R) CH 2 -O) X -H ... (1)
_{C n H m -C (= O} ) O- (CH (R) CH 2 -O) X -H ... (2)
[In the formula, n represents an integer of 8 to 20, m represents an integer of 2n-5 to 2n + 1 , R represents H, —CH ₃ , —CH ₂ —CH ₃ , and X represents 2 to 50] Represents an integer. ] The n in the general formulas (1) and (2) is an integer of 8 to 20, m is an integer of 2n-5 to 2n + 1, and X is an integer of 2 to 20. Radical polymerizable composition. The urethane (meth) acrylate (A) comprises an alkyl polyether compound (a), a polymerizable monomer (c) having a hydroxyl group and two or more polymerizable unsaturated double bonds, and an alicyclic or fatty acid. The radically polymerizable composition according to any one of claims 1 to 5 , which is a reaction product of a group-based compound (b) having two isocyanate groups. The urethane (meth) acrylate (B) is an alicyclic or aliphatic compound (b) having two isocyanate groups, a polymerizable single group having a hydroxyl group and two or more polymerizable unsaturated double bonds. The radically polymerizable composition according to any one of claims 1 to 6 , which is a reaction product with the monomer (c). Dressing consisting of radical polymerizable composition according to any one of claims 1-7. Hard coating agent comprising a radically polymerizable composition according to any one of claims 1-7. The composite_body | complex which has the film formed using the coating material of Claim 8, or the hard-coat agent of Claim 9 on the base-material surface.