KR102445218B1 - Active energy ray-curable resin composition and coating agent - Google Patents

Abstract

An active energy ray-curable resin composition containing a urethane (meth)acrylate-based composition capable of forming a cured coating film that is difficult to curl because of small curing shrinkage and is excellent in hardness and flexibility, wherein pentaerythritol and (meth)acrylic acid A urethane (meth)acrylate-based composition [I] in which a hydroxyl group of (meth)acrylate in a mixture (A) of (meth)acrylate, which is a reaction product with , The hydroxyl value of the mixture (A) provides an active energy ray-curable resin composition of 200 mgKOH/g or more.

Description

Active energy ray-curable resin composition and coating agent

The present invention relates to an active energy ray-curable resin composition and a coating agent containing a urethane (meth)acrylate-based composition, and more particularly, when a cured coating film is formed, it is difficult to curl due to small cure shrinkage, and has hardness and flexibility. It relates to an active energy ray-curable resin composition capable of forming an excellent coating film, and a coating agent using the same.

Conventionally, an active energy ray-curable resin composition is widely used as a coating agent for various substrates, an adhesive, or an anchor coat agent, etc., because curing is completed by irradiation with an active energy ray such as radiation or ultraviolet rays for a very short time. As such, urethane (meth)acrylate-based compounds and polyfunctional monomers are used. By the way, when an active energy ray-curable resin composition is used especially as a coating agent, especially as a coating agent for hard-coats, there exists a problem that cure shrinkage of a coating film occurs, and a cured coating film curls easily, and it is calculated|required that it is hard to curl.

Moreover, since the coating agent for hard-coats is used also for bent parts, such as a molded article and a display as a protective film, even if it bends the plastic film in which the cured coating film was formed, the flexibility that a crack etc. are hard to produce is calculated|required.

Curable resin composition (for example, refer patent document 1) which added inorganic fine particle to curable resin in order to suppress cure shrinkage with respect to the said thing which is hard to curl, and urethane (meth)acrylate which was made into high molecular weight as a hardening component. A curable resin composition containing A curable resin composition (for example, refer to Patent Document 3) comprising a urethane (meth)acrylate formed has been proposed.

In addition, as a method of further increasing the hardness of the hard coat layer in order to improve scratch resistance, for example, a resin composition containing dipentaerythritol hexaacrylate and tripentaerythritol octaacrylate is applied to a thickness of 80 µm. A technique is known that a film having a hardness of about 5H pencil hardness can be obtained by applying and curing the triacetylcellulose film to a film thickness of 12 µm (see, for example, Patent Document 4).

Patent Document 1 JP 2010-77292 A Patent Document 2 JP 2010-180319 A Patent Document 3 JP 2012-229412 A Patent Document 4 JP 2009-286924 A

However, in the technique disclosed in Patent Document 1, when the compatibility between the inorganic fine particles and the curable resin is taken into consideration, there is a problem that the organic solvent that can be used is limited or the possibility that the surface abnormality of the coating film is increased, and generally inorganic Since microparticles|fine-particles are expensive, resin and paint which mix|blended them also became expensive, and in reality, the use of curable resin was limited to special uses.

In addition, in the disclosed technology of Patent Document 2, the manufacturing method for increasing the molecular weight of urethane (meth)acrylate used as a curing component is a multi-step reaction, so operation is complicated or the scratch resistance of the coating film is reduced. .

On the other hand, in the technique disclosed in Patent Document 3, a cured coating film having small cure shrinkage and suppressed curl can be obtained, but it is insufficient from the viewpoint of hardness.

Further, in the technique disclosed in Patent Document 4, although the surface hardness of the cured coating film is high, the curl generated during curing is large, and since it is hard and brittle, cracks occur when the coating film is bent.

Therefore, in the present invention, under such a background, when a cured coating film is formed, it is difficult to curl because curing shrinkage is small, and on the other hand, an activity containing a urethane (meth)acrylate-based composition capable of forming a coating film excellent in hardness and flexibility. An energy ray-curable resin composition and a coating agent using the same are provided.

However, the present inventors have conducted intensive research in view of such circumstances, and as a result, the reaction product of at least one of pentaerythritol and dipentaerythritol and (meth)acrylic acid as a curing component shows a hydroxyl value within a specific range, By using a urethane (meth)acrylate-based composition made by reacting the hydroxyl group of (meth)acrylate in the reactant with polyvalent isocyanate, it is difficult to curl due to small cure shrinkage, and a cured coating film excellent in hardness and flexibility can be obtained. found that there is

That is, the first aspect of the present invention is a mixture (A) of the following (meth)acrylates (a1) to (a4), which are reactants of pentaerythritol and (meth)acrylic acid, (meth)acrylates (a1) to ( It relates to an active energy ray-curable resin composition containing a3) and a urethane (meth)acrylate-based composition [I] in which the polyvalent isocyanate (CA) reacted, and the hydroxyl value of the mixture (A) is 200 mgKOH/g or more.

Mixture (A)

(a1) pentaerythritol mono (meth) acrylate

(a2) pentaerythritol di(meth)acrylate

(a3) pentaerythritol tri (meth) acrylate

(a4) pentaerythritol tetra (meth) acrylate

In addition, the second aspect of the present invention is the urethane (meth)acrylate-based composition [I], and the following (meth)acrylates (b1) to (b6) which are reactants of dipentaerythritol and (meth)acrylic acid. ) containing urethane (meth)acrylate-based composition [II] in which (meth)acrylates (b1) to (b5) in the mixture (B) and polyvalent isocyanate (CB) reacted, the mixture (B) It is related with the active energy ray-curable resin composition whose hydroxyl value is 40 mgKOH/g or more.

mixture (B)

(b1) dipentaerythritol mono (meth) acrylate

(b2) dipentaerythritol di(meth)acrylate

(b3) dipentaerythritol tri(meth)acrylate

(b4) dipentaerythritol tetra(meth)acrylate

(b5) dipentaerythritol penta (meth) acrylate

(b6) dipentaerythritol hexa(meth)acrylate

Further, the third aspect of the present invention is the following [α] (meth)acrylates (a1) to (a3), the following [β] (meth)acrylates (b1) to (b5), and, It is related with the active energy ray-curable resin composition containing the urethane (meth)acrylate type composition [III] which polyhydric isocyanate (CC) reacted.

[α] The hydroxyl value of the mixture (A) of the following (meth)acrylates (a1) to (a4), which is a reaction product of pentaerythritol and (meth)acrylic acid, is 200 mgKOH/g or more, and in the mixture (A) (meth)acrylates (a1) to (a3).

(a1) pentaerythritol mono (meth) acrylate

(a2) pentaerythritol di(meth)acrylate

(a3) pentaerythritol tri (meth) acrylate

(a4) pentaerythritol tetra (meth) acrylate

[β] The hydroxyl value of the mixture (B) of the following (meth)acrylates (b1) to (b6), which is a reaction product of dipentaerythritol and (meth)acrylic acid, is 40 mgKOH/g or more, and the mixture (B) (meth)acrylates in (b1) to (b5).

(b1) dipentaerythritol mono (meth) acrylate

(b2) dipentaerythritol di(meth)acrylate

(b3) dipentaerythritol tri(meth)acrylate

(b4) dipentaerythritol tetra(meth)acrylate

(b5) dipentaerythritol penta (meth) acrylate

(b6) dipentaerythritol hexa(meth)acrylate

Moreover, in this invention, the coating agent containing the said active energy ray-curable resin composition is also provided.

Since the active energy ray-curable resin composition as in the first aspect of the present invention has a small cure shrinkage, it is difficult to curl, and a cured coating film excellent in hardness and flexibility can be formed, and a coating film surface that is tack-free even in the coating film before curing is formed. It can do this, and it is especially useful for various uses, such as a coating agent for hard-coats.

In addition, the active energy ray-curable resin composition as in the second aspect of the present invention has a small curing shrinkage, so it is difficult to curl, and it is possible to form a cured coating film excellent in hardness and flexibility. Useful for branches.

In addition, the active energy ray-curable resin composition as in the third aspect of the present invention has a small cure shrinkage, so it is difficult to curl, and it is possible to form a cured coating film excellent in hardness, flexibility and scratch resistance, especially for hard coats. It is useful for various uses, such as a coating agent.

When the content ratio of pentaerythritol di(meth)acrylate (a2) in the mixture (A) of the (meth)acrylates (a1) to (a4) is 10 to 50% by weight, the viewpoint of coexistence of hardness and flexibility to excel in

If the content ratio of pentaerythritol di(meth)acrylate (a2) with respect to the total of the (meth)acrylates (a1) to (a3) is 15 to 55% by weight, from the viewpoint of coexistence of hardness and flexibility, excellent do.

If the weight average molecular weight of the said urethane (meth)acrylate type composition [I] is 1,000-20,000, it will become excellent in the easiness of handling of an active energy ray-curable resin composition.

When the content ratio of dipentaerythritol penta(meth)acrylate (b5) in the mixture (B) of the (meth)acrylates (b1) to (b6) is 15 to 60% by weight, it is necessary to achieve both hardness and flexibility. become even better

When the content ratio of dipentaerythritol penta(meth)acrylate (b5) to the total of the (meth)acrylates (b1) to (b5) is 45 to 90% by weight, it is further excellent in coexistence of hardness and flexibility.

When the content ratio of dipentaerythritol tetra(meth)acrylate (b4) in the mixture (B) of the (meth)acrylates (b1) to (b6) is 1 to 35% by weight, the flexibility is excellent.

When the content ratio of dipentaerythritol tetra(meth)acrylate (b4) to the total of the (meth)acrylates (b1) to (b5) is 2 to 40% by weight, the flexibility is further improved.

When the weight average molecular weight of the said urethane (meth)acrylate type composition [II] is 1,000-20,000, it becomes excellent in the easiness of handling of an active energy ray-curable resin composition.

When the weight average molecular weight of the urethane (meth)acrylate-based composition [III] is 1,000 to 20,000, the easiness of handling of the active energy ray-curable resin composition is further improved.

Hereinafter, the present invention will be described in detail.

In the present invention, (meth)acryl means acryl or methacryl, (meth)acryloyl means acryloyl or methacryloyl, and (meth)acrylate means acrylate or methacrylate, respectively.

The active energy ray-curable resin composition of the present invention includes the following urethane (meth)acrylate-based composition [I], urethane (meth)acrylate-based composition [I] and [II] and urethane (meth)acrylate-based composition [III] It is characterized in that it contains any one urethane (meth)acrylate-based composition selected from the group consisting of ], and there are three aspects.

The urethane (meth)acrylate-based composition [I] is (meth)acryl in the mixture (A) of the following (meth)acrylates (a1) to (a4), which are reactants of pentaerythritol and (meth)acrylic acid. It is formed by reacting the rates (a1) to (a3) with polyvalent isocyanate (CA), and the hydroxyl value of the mixture (A) is 200 mgKOH/g or more.

Mixture (A)

(a1) pentaerythritol mono (meth) acrylate

(a2) pentaerythritol di(meth)acrylate

(a3) pentaerythritol tri (meth) acrylate

(a4) pentaerythritol tetra (meth) acrylate

The urethane (meth)acrylate-based composition [II] is (meth) in the mixture (B) of the following (meth)acrylates (b1) to (b6), which are reactants of dipentaerythritol and (meth)acrylic acid. Acrylates (b1) to (b5) and polyvalent isocyanate (CB) are reacted, and the hydroxyl value of the mixture (B) is 40 mgKOH/g or more.

mixture (B)

(b1) dipentaerythritol mono (meth) acrylate

(b2) dipentaerythritol di(meth)acrylate

(b3) dipentaerythritol tri(meth)acrylate

(b4) dipentaerythritol tetra(meth)acrylate

(b5) dipentaerythritol penta (meth) acrylate

(b6) dipentaerythritol hexa(meth)acrylate

The urethane (meth)acrylate-based composition [III] is (meth)acrylates (a1) to (a3) which are the following [α], (meth)acrylates (b1) to (b5) which are the following [β], and polyvalent isocyanate (CC) reacted.

[α] The hydroxyl value of the mixture (A) of the following (meth)acrylates (a1) to (a4), which is a reaction product of pentaerythritol and (meth)acrylic acid, is 200 mgKOH/g or more, and in the mixture (A) (meth)acrylates (a1) to (a3).

(a1) pentaerythritol mono (meth) acrylate

(a2) pentaerythritol di(meth)acrylate

(a3) pentaerythritol tri (meth) acrylate

(a4) pentaerythritol tetra (meth) acrylate

[β] The hydroxyl value of the mixture (B) of the following (meth)acrylates (b1) to (b6), which is a reaction product of dipentaerythritol and (meth)acrylic acid, is 40 mgKOH/g or more, and the mixture (B) (meth)acrylates in (b1) to (b5).

(b1) dipentaerythritol mono (meth) acrylate

(b2) dipentaerythritol di(meth)acrylate

(b3) dipentaerythritol tri(meth)acrylate

(b4) dipentaerythritol tetra(meth)acrylate

(b5) dipentaerythritol penta (meth) acrylate

(b6) dipentaerythritol hexa(meth)acrylate

<Urethane (meth)acrylate-based composition [I]>

First, the urethane (meth)acrylate-based composition [I] will be described.

In the present invention, the hydroxyl value of the mixture (A) of the (meth)acrylates (a1) to (a4) obtained by reacting the pentaerythritol with (meth)acrylic acid is 200 mgKOH/g or more, and is preferably 200 mgKOH/g or more. Preferably 210 to 380 mgKOH/g, particularly preferably 230 to 320 mgKOH/g.

When the hydroxyl value of such a mixture (A) is too small, since the weight average molecular weight of the urethane (meth)acrylate-based composition [III] decreases, curing shrinkage at the time of curing becomes large, so the tendency to curl easily Moreover, there exists a tendency for a flexibility to fall. Moreover, since a viscosity improves with the increase of molecular weight when the said hydroxyl value becomes too large normally, there exists a tendency for handling to become difficult.

The hydroxyl value in this invention can be calculated|required by the method according to JISK0070 1992.

Moreover, in this invention, it is hardness that the content rate of pentaerythritol di(meth)acrylate (a2) in the mixture (A) of the said (meth)acrylates (a1) - (a4) is 10 to 50 weight% It is preferable from a viewpoint of coexistence of a flexibility and flexibility, Especially preferably, it is 15 to 45 weight%, More preferably, it is 20 to 40 weight%. When such a content ratio is too small, there exists a tendency for a flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.

Moreover, it is from a viewpoint of coexistence of hardness and flexibility that the content rate of pentaerythritol di(meth)acrylate (a2) with respect to the said (meth)acrylate (a1)-(a3) total is 15 to 55 weight% Preferably, it is 20 to 50 weight% especially preferably, More preferably, it is 25 to 45 weight%. When such a content ratio is too small, there exists a tendency for a flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.

In the present invention, pentaerythritol and (meth)acrylic acid are reacted to prepare a (meth)acrylic acid adduct of pentaerythritol, but the reaction of pentaerythritol and (meth)acrylic acid is carried out by a known general method. can do. In this reaction, pentaerythritol mono (meth) acrylate (a1) with one (meth) acrylic acid added to pentaerythritol, pentaerythritol di (meth) acrylate (a2) with two added (a2), three A mixture (A) containing the added pentaerythritol tri(meth)acrylate (a3) and four added pentaerythritol tetra(meth)acrylates (a4) is obtained, and has the above hydroxyl value as a whole. Mixture (A) can be obtained.

In addition, side reaction products, such as a Michael adduct of acrylic acid, may be contained in the said mixture (A).

In the case of adjustment of a hydroxyl value, it can implement by adjusting the content rate of (meth)acrylate (a1) - (a4), for example.

In the present invention, the polyvalent isocyanate (CA) reacts with the (meth)acrylates (a1) to (a3), and specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane Aromatic polyisocyanates, such as polyisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate; Aliphatic polyisocyanates such as triisocyanate; alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate and norbornene diisocyanate; or a trimer compound or a large amount of these polyisocyanates Sieve compound, arophanate type polyisocyanate, biuret type polyisocyanate, water dispersion type polyisocyanate (for example, "Aquanate 105", "Aquanate 120", "Aquanate 210" manufactured by Tosoh Corporation), etc. can be heard These can be used individually or in combination of 2 or more types.

Among these, alicyclic polyisocyanate and aromatic polyisocyanate are preferable from the viewpoint of strength, and isophorone diisocyanate, hydrogenated xylene diisocyanate, xylene diisocyanate and tolylene diisocyanate are particularly preferable.

In the present invention, the urethane (meth)acrylate-based composition [I] comprises a hydroxyl group of (meth)acrylates (a1) to (a3) in the mixture (A) of the (meth)acrylates (a1) to (a4); It can be obtained by reacting the isocyanate group of the polyvalent isocyanate (CA). In this case, in the urethane (meth)acrylate-based composition [I], (meth)acrylate (a1) and polyvalent isocyanate (CA) reacted, (meth)acrylate (a2) and polyvalent isocyanate (CA) It contains the reacted, (meth)acrylate (a3) and polyvalent isocyanate (CA) reacted, and does not participate in the reaction or unreacted product of (meth)acrylate (a1) to (a3) in the system. (meth)acrylate (a4) etc. which do not come to be contained.

In the reaction of (meth)acrylates (a1) to (a3) and polyvalent isocyanate (CA), the functional group molar ratio of a hydroxyl group and an isocyanate group is adjusted, and it can carry out using the reaction catalyst mentioned later as needed.

When there are two isocyanate groups of polyhydric isocyanate (CA), the preparation reaction molar ratio of such a polyhydric isocyanate (CA) and the mixture (A) of (meth)acrylates (a1)-(a4) is polyhydric isocyanate (CA) : It is preferable that the (meth)acrylate mixture (A) is 1:1-1:5, Especially preferably, it is 1:1-1:3, More preferably, it is 1:1-1:2.

When the proportion of the mixture (A) is too large, the amount of low molecular weight monomer increases and the curing shrinkage increases, so curl tends to become large. When the proportion of the mixture (A) is too small, unreacted polyisocyanate (CA) remains, and the stability and safety of the cured coating film tend to decrease.

The reaction of the (meth)acrylates (a1) to (a3) and the polyvalent isocyanate (CA) in the (meth)acrylate mixture (A) is usually carried out by placing the mixture (A) and the polyvalent isocyanate (CA) in a reactor at once or separately. It can be put separately to react.

In the above reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction. Examples of such a catalyst include dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, Organometallic compounds such as zinc bisacetylacetate, zirconium tris(acetylacetate)ethylacetacetate, and zirconiumtetraacetylacetate; tin octylate, tin octhenate, zinc hexanoate, zinc octhenate, zinc stearate, 2-ethyl Metal salts such as zirconium hexanoate, cobalt naphthenate, stannous chloride, stannic chloride, and potassium acetate; triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2 ]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N',N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine Amine catalysts, such as Pauline; Bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc., organic bismuth compounds, such as dibutylbismuth dilaurate and dioctylbismuth dilaurate, 2-ethylhexanoic acid bismuth salt, naphthenic acid bismuth salt, isodecanic acid bismuth salt, neodecanoic acid bismuth salt, lauric acid bismuth salt, milate bismuth salt, stearic acid bismuth salt, oleic acid bismuth salt, linoleic acid bismuth salt, bismuth acetate salt, bismuth ribs neodecanoate and bismuth catalysts such as organic acid bismuth salts such as disalicylic acid bismuth salt and dimolaric acid bismuth salt. Among these, dibutyltin dilaurate, 1,8-diazabicyclo[5,4,0] Undecene is very suitable. These can be used individually or in combination of 2 or more types.

Moreover, in the said reaction, it is preferable to use a polymerization inhibitor further. As said polymerization inhibitor, the well-known general thing used as a polymerization inhibitor can be used, For example, p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone. , quinones such as 2,5-di-t-butylhydroquinone, methylhydroquinone and mono-t-butylhydroquinone, aromatics such as 4-methoxyphenol and 2,6-di-t-butylcresol; p-t-butylcatechol etc. are mentioned. Among them, aromatics are preferable, and 4-methoxyphenol and 2,6-di-t-butylcresol are particularly preferable. These can be used individually or in combination of 2 or more types.

In the above reaction, an organic solvent having no functional group reacting with the isocyanate group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene Organic solvents, such as solvents, can be used. These can be used individually or in combination of 2 or more types.

The reaction temperature is usually 30 to 90°C, preferably 40 to 80°C, and the reaction time is usually 4 to 72 hours, preferably 8 to 48 hours.

In this way, the urethane (meth)acrylate-based composition [I] used in the present invention is obtained.

As a weight average molecular weight of such a urethane (meth)acrylate type composition [I], it is preferable that it is 1,000-20,000, Especially preferably, it is 2,000-18,000, More preferably, it is 3,000-16,000. When such a weight average molecular weight is too small, there exists a tendency for a cured coating film to become brittle, and when too large, there exists a tendency which becomes high viscosity and becomes difficult to handle.

In addition, the said weight average molecular weight is a weight average molecular weight in conversion of standard polystyrene molecular weight, and, in a high performance liquid chromatograph (manufactured by Waters, "ACQUITY APC System"), column: ACQUITY APC XT450 1 piece, ACQUITY APC XT200 1 piece , ACQUITY APC XT45 is measured by using two total of four in series.

The content of the urethane (meth)acrylate in the urethane (meth)acrylate-based composition [I] is preferably 50% by weight or more, particularly preferably 60% by weight or more, more preferably 70% by weight or more, Especially preferably, it is 80 weight% or more. In addition, the upper limit is usually 95% by weight.

<Urethane (meth)acrylate-based composition [II]>

Next, the urethane (meth)acrylate type composition [II] is demonstrated.

In the present invention, the hydroxyl value of the mixture (B) of the (meth)acrylates (b1) to (b6) obtained by reacting the dipentaerythritol with (meth)acrylic acid is 40 mgKOH/g or more, and is preferably Preferably it is 43-130 mgKOH/g, Especially preferably, it is 45-125 mgKOH/g, More preferably, it is 70-120 mgKOH/g.

When the hydroxyl value of such a mixture (B) is too small, the content of dipentaerythritol hexa (meth) acrylate (b6) that does not react with isocyanate due to a low molecular weight and a large number of ethylenically unsaturated groups increases, Since cure shrinkage at the time of hardening becomes large, it exists in the tendency for curling to become easy, and there exists a tendency for a flexibility to fall. Moreover, since a viscosity improves normally with the increase of molecular weight when the said hydroxyl value becomes too large, there exists a tendency for handling to become difficult.

In the present invention, the content ratio of dipentaerythritol penta(meth)acrylate (b5) in the mixture (B) of the (meth)acrylates (b1) to (b6) is 15 to 60% by weight, It is preferable from a viewpoint of compatibility of flexibility, Especially preferably, it is 20 to 55 weight%, More preferably, it is 25 to 55 weight%. When such a content ratio is too small, there exists a tendency for a flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.

It is preferable from the viewpoint of coexistence of hardness and flexibility that the content ratio of dipentaerythritol penta(meth)acrylate (b5) with respect to the total of the (meth)acrylates (b1) to (b5) is 45 to 90% by weight. and particularly preferably 50 to 90% by weight, more preferably 55 to 90% by weight. When such a content ratio is too small, there exists a tendency for a flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.

It is preferable from the viewpoint of flexibility that the content ratio of dipentaerythritol tetra(meth)acrylate (b4) in the mixture (B) of the (meth)acrylates (b1) to (b6) is 1 to 35% by weight, , particularly preferably 2 to 30% by weight, more preferably 3 to 25% by weight. When such a content ratio is too small, there exists a tendency for a flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.

It is preferable from the viewpoint of flexibility that the content ratio of dipentaerythritol tetra(meth)acrylate (b4) to the total of the (meth)acrylates (b1) to (b5) is 2 to 40% by weight, and particularly preferably Preferably it is 3 to 35 weight%, More preferably, it is 4 to 30 weight%. When such a content ratio is too small, there exists a tendency for a flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.

In the present invention, dipentaerythritol and (meth)acrylic acid are reacted to prepare a (meth)acrylic acid adduct of dipentaerythritol. However, in the reaction between dipentaerythritol and (meth)acrylic acid, a known general can be carried out by the method of In this reaction, dipentaerythritol mono (meth) acrylate (b1) with one (meth) acrylic acid added to dipentaerythritol, dipentaerythritol di (meth) acrylate with two added (meth) acrylate ( b2), three added dipentaerythritol tri(meth)acrylate (b3), four added dipentaerythritol tetra(meth)acrylate (b4), five added dipentaerythritol penta(meth) ) acrylate (b5), a mixture (B) containing six added dipentaerythritol hexa (meth)acrylate (b6) can be obtained, and the mixture (B) satisfying the above hydroxyl value as a whole can be obtained

In addition, side reaction products, such as the Michael adduct of acrylic acid, may be contained in the said mixture (B).

In the case of adjustment of a hydroxyl value, it can carry out by adjusting the content rate of (meth)acrylate (b1) - (b6), for example.

In the present invention, the polyvalent isocyanate (CB) reacts with the (meth)acrylates (b1) to (b5), and specifically, the same as the polyvalent isocyanate (CA) described above can be exemplified. The polyvalent isocyanate (CB) may be the same as or different from the polyvalent isocyanate (CA).

In addition, the polyisocyanate (CB) may be a reaction product of the polyisocyanate and a polyol. As such a polyol, for example, a low molecular weight polyol or a high molecular weight polyol, specifically, a polyether-based polyol, a polyester-based polyol, a polycarbonate-based polyol, a polybutadiene-based polyol, ethylene/isoprene/butadiene, or the like is reacted. and polyolefin-based polyols or their hydrogenated products, polyolefin-based polyols other than those described above, and (meth)acrylic-based polyols.

Of these polyvalent isocyanates (CB), alicyclic polyisocyanates and aromatic polyisocyanates are preferable from the viewpoint of weather resistance and strength, and particularly preferably isophorone diisocyanate, hydrogenated xylene diisocyanate, xylene diisocyanate, and tolyl. It is rendiisocyanate.

In the present invention, the urethane (meth)acrylate-based composition [II] comprises a hydroxyl group of (meth)acrylates (b1) to (b5) in the mixture (B) of the (meth)acrylates (b1) to (b6) , It can be obtained by reacting the isocyanate group of the polyvalent isocyanate (CB). In this case, in urethane (meth)acrylate-based composition [II], (meth)acrylate (b1) and polyvalent isocyanate (CB) reacted, (meth)acrylate (b2) and polyvalent isocyanate (CB) What reacted, (meth)acrylate (b3) and polyvalent isocyanate (CB) reacted, (meth)acrylate (b4) and polyvalent isocyanate (CB) reacted, (meth)acrylate (b5) and polyvalent isocyanate (CB) are contained, and the system also contains unreacted substances of (meth)acrylates (b1) to (b5) and (meth)acrylates (b6) that do not participate in the reaction. do.

The preparative reaction molar ratio of such polyvalent isocyanate (CB) and the mixture (B) of (meth)acrylates (b1) to (b6) is, for example, when there are two isocyanate groups of polyvalent isocyanate (CB), polyvalent Isocyanate (CB): It is preferable that the (meth)acrylate mixture (B) is 1:1-1:5, Especially preferably, 1:1-1:4, More preferably, 1:1-1:3 to be.

When the proportion of the mixture (B) is too large, curl tends to increase because the amount of low molecular weight monomer increases and cure shrinkage becomes large. When the proportion of the mixture (B) is too small, unreacted polyisocyanate (CB) There exists a tendency for stability and safety|security of a cured coating film to fall by remaining.

The reaction of the (meth)acrylates (b1) to (b5) and the polyvalent isocyanate (CB) in the (meth)acrylate mixture (B) is usually the mixture (B) and the polyvalent isocyanate (CB) in a reactor at once or It can be prepared separately and reacted.

In the above reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction. Examples of such a catalyst include those described in the urethane (meth)acrylate-based composition [I].

Moreover, in the said reaction, also when using the polymerization inhibitor and the organic solvent which does not have a functional group reactive with respect to an isocyanate group, the thing similar to what was demonstrated with the said urethane (meth)acrylate type composition [I] can be illustrated.

Moreover, in preparation of the urethane (meth)acrylate type composition [II], it can carry out according to preparation of the said urethane (meth)acrylate type composition [I].

In this way, the urethane (meth)acrylate-based composition [II] used in the present invention is obtained.

As a weight average molecular weight of such a urethane (meth)acrylate type composition [II], it is preferable that it is 1,000-20,000, More preferably, it is 1,500-18,000, Especially preferably, it is 2,000-16,000. When such a weight average molecular weight is too small, there exists a tendency for a cured coating film to become brittle, and when too large, there exists a tendency which becomes high viscosity and becomes difficult to handle.

In addition, the measuring method of said weight average molecular weight is the same as the said measuring method.

It is preferable that the viscosity at 60 degreeC of such a urethane (meth)acrylate type composition [II] is 1,000-300,000 mPa*s, Especially preferably, 1,500-200,000 ma*s, More preferably, it is 2,000-100,000 mPa·s. If such a viscosity is outside the said range, there exists a tendency for coatability to fall.

In addition, the measuring method of the viscosity in 60 degreeC is based on an E-type viscometer.

The content of the urethane (meth)acrylate in the urethane (meth)acrylate-based composition [II] is preferably 35% by weight or more, particularly preferably 40% by weight or more, more preferably 45% by weight or more, Especially preferably, it is 50 weight% or more, More preferably, it is 60 weight% or more. In addition, an upper limit is 95 weight% normally.

<Urethane (meth)acrylate-based composition [III]>

Moreover, urethane (meth)acrylate type composition [III] is demonstrated.

<Mixture (A)>

First, the mixture (A) containing the (meth)acrylates (a1)-(a3) which is a constituent material of a urethane (meth)acrylate type composition [III] is demonstrated.

The mixture (A) is a mixture of the (meth)acrylates (a1) to (a4) obtained by reacting the pentaerythritol with (meth)acrylic acid, and the hydroxyl value thereof is 200 mgKOH/g or more, Preferably it is 210-380 mgKOH/g, Especially preferably, it is 230-320 mgKOH/g.

As for the said mixture (A), the thing similar to what was demonstrated by the said urethane (meth)acrylate type composition [I] can be illustrated.

In the mixture (A), (meth)acrylates (a1) to (a3) having a hydroxyl group react with polyisocyanate (CC) described later.

<Mixture (B)>

Next, the mixture (B) containing the (meth)acrylates (b1)-(b5) which is a constituent material of a urethane (meth)acrylate type composition [III] is demonstrated. The mixture (B) is a mixture of the (meth)acrylates (b1) to (b6) obtained by reacting the dipentaerythritol with (meth)acrylic acid, and the hydroxyl value is 40 mgKOH/g or more, Preferably it is 43-130 mgKOH/g, Especially preferably, it is 45-125 mgKOH/g, More preferably, it is 70-120 mgKOH/g.

About the said mixture (B), the thing similar to what was demonstrated with the said urethane (meth)acrylate type composition [II] can be illustrated.

In the mixture (B), (meth)acrylates (b1) to (b5) having a hydroxyl group react with the following polyvalent isocyanate (CC).

<Polyvalent isocyanate (CC)>

Next, polyhydric isocyanate (CC) which is a constituent material of urethane (meth)acrylate type composition [III] is demonstrated.

In the present invention, the polyvalent isocyanate (CC) is a hydroxyl group-containing (meth)acrylate, that is, the (meth)acrylates (a1) to (a3) and (meth)acrylates (b1) to (b5) react with Specifically, examples such as the polyvalent isocyanate (CA) described in the urethane (meth)acrylate-based composition [I], and the polyvalent isocyanate (CB) described in the urethane (meth)acrylate-based composition [II] can do. The polyvalent isocyanate (CC) may be the same as or different from the polyvalent isocyanate (CA) or polyvalent isocyanate (CB).

Moreover, the said polyhydric isocyanate (CC), the said polyhydric isocyanate (CA), and polyhydric isocyanate (CB) are collectively called "polyhydric isocyanate (C)."

In the present invention, the hydroxyl group of (meth)acrylates (a1) to (a3) in the mixture (A) of the (meth)acrylates (a1) to (a4), and the (meth)acrylates (b1) to ( A urethane (meth)acrylate-based composition [III] can be obtained by reacting the hydroxyl group of the (meth)acrylates (b1) to (b5) in the mixture (B) of b6) and the isocyanate group of the polyvalent isocyanate (CC) have. In this case, in urethane (meth)acrylate-based composition [III], (meth)acrylate (a1) and polyvalent isocyanate (CC) reacted, (meth)acrylate (a2) and polyvalent isocyanate (CC) What was reacted, (meth)acrylate (a3) and polyvalent isocyanate (CC) reacted, (meth)acrylate (b1) and polyvalent isocyanate (CC) reacted, (meth)acrylate ( b2) and polyvalent isocyanate (CC) reacted, (meth)acrylate (b3) and polyvalent isocyanate (CC) reacted, (meth)acrylate (b4) and polyvalent isocyanate (CC) reacted , (meth)acrylate (b5) and polyvalent isocyanate (CC) reacted, (a1) to (a3) and (meth)acrylates (b1) to (b5) were mixed and reacted with polyvalent isocyanate (CC) (meth)acrylates (a4) which do not participate in the reaction or unreacted substances of (meth)acrylates (a1) to (a3) and (b1) to (b5) in the system; (b6), etc. will also be contained.

Regarding the reaction of (meth)acrylates (a1) to (a3) and (meth)acrylates (b1) to (b5) with polyvalent isocyanate (CC), the molar ratio of the functional groups of the hydroxyl group and the isocyanate group is adjusted, and if necessary It can carry out using the reaction catalyst mentioned later.

The preparative reaction molar ratio of such a mixture (A) of (meth)acrylates (a1) to (a4), and a mixture (B) of (meth)acrylates (b1) to (b6) and polyvalent isocyanate (CC) is, When there are two isocyanate groups of polyhydric isocyanate (CC), polyhydric isocyanate (CC): The sum total of (meth)acrylate mixture (A) and (meth)acrylate mixture (B) is 1:1 - 1:5 It is preferable, Especially preferably 1:1-1:3, More preferably, it is 1:1-1:2. Moreover, in (meth)acrylate mixture (A): (meth)acrylate mixture (B) double *, it is preferable that it is 90:10-10:90, Especially preferably, 70:30-15:85, and further Preferably it is 50:50-20:80.

When the ratio of the total of the mixture (A) and the mixture (B) to the polyvalent isocyanate (CC) is too large, the amount of low molecular weight monomer increases and the curing shrinkage increases, so curl tends to become large, and the mixture (A) and the mixture When there are too few ratios of the sum total of (B), unreacted polyvalent isocyanate (CC) will remain|survive and there exists a tendency for stability and safety|security of a cured coating film to fall.

When the ratio of the mixture (B) to the mixture (A) is too large, the low molecular weight monomers increase and the curing shrinkage becomes large, so curl tends to become large, and when the ratio of the mixture (B) is too small, the hardness and abrasion resistance tends to decrease.

(meth)acrylates (a1) to (a3) in (meth)acrylate mixture (A) and (meth)acrylates (b1) to (b5) in (meth)acrylate mixture (B) and polyvalent isocyanate (CC ), the mixture (A), the mixture (B), and the polyvalent isocyanate (CC) can be reacted by putting them together or separately in a reactor.

In the above reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction, and examples of such a catalyst include those described in the urethane (meth)acrylate-based composition [I].

Moreover, in the said reaction, the thing similar to what was demonstrated with the said urethane (meth)acrylate type composition [I] can be illustrated also when using the polymerization inhibitor and the organic solvent which does not have a functional group which reacts with respect to an isocyanate group.

Moreover, in preparation of a urethane (meth)acrylate type composition [III], it can carry out according to preparation of the said urethane (meth)acrylate type composition [I].

In this way, the (meth)acrylates (a1) to (a3) of [α], the (meth)acrylates (b1) to (b5) of [β], and the polyvalent isocyanate (CC) are reacted. A urethane (meth)acrylate-based composition [III] can be obtained.

In this invention, a polyol is also made to contain, and it is made to react with polyhydric isocyanate (CC), (meth)acrylates (a1) - (a3) of [α], (meth)acrylates (b1) of [β] - (b5), a urethane (meth)acrylate-based composition [III] comprising a polyvalent isocyanate (CC) and a polyol is obtained.

As the polyol, for example, low molecular weight polyol or high molecular weight polyol, specifically, polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol obtained by reacting ethylene/isoprene/butadiene, etc. Or polyols, such as its hydride, polyolefin-type polyol other than the above, and (meth)acrylic-type polyol, etc. are mentioned.

The weight average molecular weight of such urethane (meth)acrylate composition [III] is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, particularly preferably 3,000 to 12,000, and particularly preferably 4,000 to 10,000. . When such a weight average molecular weight is too small, there exists a tendency for a cured coating film to become brittle, and when too large, there exists a tendency which becomes high viscosity and becomes difficult to handle.

In addition, the said weight average molecular weight is a weight average molecular weight by conversion of standard polystyrene molecular weight, and in a high performance liquid chromatograph (Waters company wph, "ACQUITY APC system"), column: ACQUITY APC XT450 1, ACQUITY APC XT200 1 Dog, ACQUITY APC XT45 is measured by using two total of four in series.

The content of the urethane (meth)acrylate in the urethane (meth)acrylate-based composition [III] is preferably 50% by weight or more, particularly preferably 60% by weight or more, more preferably 70% by weight or more, Especially preferably, it is 80 weight% or more. In addition, an upper limit is 95 weight% normally.

<Active energy ray-curable resin composition>

The active energy ray-curable resin composition of the present invention includes the first aspect (invention according to the first aspect) containing the urethane (meth)acrylate-based composition [I], and the urethane (meth)acrylate-based composition [I] ] and the second aspect (invention according to the second aspect) containing the urethane (meth)acrylate composition [II], and the third aspect (the third aspect) containing the urethane (meth)acrylate composition [III] invention to the gist).

The active energy ray-curable resin composition which is a said 2nd aspect contains a urethane (meth)acrylate type composition [I] and a urethane (meth)acrylate type composition [II] as mentioned above. About the content ratio ([I]/[II]) of such urethane (meth)acrylate-type composition [I] and urethane (meth)acrylate-type composition [II], it is 90/10-10/90 by weight ratio , particularly preferably 87/13 to 20/80, more preferably 85/15 to 30/70, particularly preferably 80/20 to 55/45, still more preferably 80/20 to 65/ 35. When such a content rate is too small, there exists a tendency for a flexibility to fall, and when too large, there exists a tendency for hardness to become inadequate.

It is preferable to further contain a photoinitiator (D) in the active-energy-ray-curable resin composition (it abbreviates as a "resin composition" hereafter) of this invention of said 1st - 3rd aspect. In addition, within the range that does not impair the effects of the present invention, other urethane (meth) acrylates, ethylenically unsaturated monomers other than urethane (meth) acrylate, acrylic resins, surface conditioners, labeling agents, polymerization inhibitors, etc. may be added. and also fillers, dyes, pigments, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, gelling agents, stabilizers, defoamers, surfactants, labeling agents, thixotropic agents, antioxidants, flame retardants, antistatic agents, It is also possible to blend a filler, a reinforcing agent, a light remover, a crosslinking agent, silica, silica, water-dispersed or solvent-dispersed silica, a zirconium compound, a preservative, and the like.

Examples of the photopolymerization initiator (D) include diethoxyacetphenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 4-(2-hydroxyethoxy)phenyl. -(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1- Propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methyl-propane, 2-methyl-2- Morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4 Acetphenones such as -(1-methylvinyl)phenyl]propanone oligomer; Benzoins, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone; Methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2, 4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethyl Benzophenones such as ammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-pro thioxanthone such as poxythioxanthone and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethyl Benzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bissa(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. of acylphosphine oxides; oxime esters such as 1.2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyloxime)], and the like. In addition, only 1 type of these photoinitiators (D) may be used independently and 2 or more types may be used together.

Among these, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoyl isopropyl ether, 4-(2-hydroxyethoxy)-phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy- Preference is given to using 2-methyl-1-phenyl propan-1-one.

In addition, as these auxiliary agents, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Mihiraketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4 -Dimethylaminobenzoate ethyl, 4-dimethylaminobenzoic acid (n-butoxy)ethyl, 4-dimethylaminobenzoate isoamyl, 4-dimethylaminobenzoate 2-ethylhexyl, 2,4-diethylthioxanthone, 2,4 - It is also possible to use diisopropylthioxanthone or the like in combination. These can be used individually or in combination of 2 or more types.

As content of a photoinitiator (D), it is preferable that it is 0.1-20 weight part with respect to 100 weight part of hardening components contained in a resin composition, Especially preferably, it is 0.5-10 weight part, More preferably, it is 1-10 weight part. to be. When the content of the photopolymerization initiator (D) is too small, curing tends to be poor and film formation tends to be difficult.

As an ethylenically unsaturated monomer other than urethane (meth)acrylate, a monofunctional monomer, a bifunctional monomer, and a trifunctional or more than trifunctional polyfunctional monomer are mentioned, for example. These can be used individually or in combination of 2 or more types.

Examples of such monofunctional monomers include styrene-based monomers such as styrene, vinyltoluene, chlorostarene, and α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, acrylonitrile, 2- Methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate , 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dish Clopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl )-methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) -methyl (meth) acrylate, 3-ethyl-3-oxetanyl methyl (meth) acryl rate, γ-butyrolactone (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) ( Meth) acrylate, nonylphenol propylene oxide modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate Half (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) ) (meth) acrylate, aryl (meth) acrylate, (meth) acryloyl morpholine, polyoxyethylene secondary alkyl ether acrylate, etc. An acrylate type monomer, 2-hydroxyethyl acrylamide, N-methylol (meth)acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, vinyl acetate, etc. are mentioned.

As such a bifunctional monomer, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene Glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide Modified bisphenol A di(meth)acrylate, propylene oxide Modified bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, ethoxylated cyclohexanedimethanol di(meth)acrylate, dimethyloldi Cyclopentane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate Acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxy pivalic acid Modified neopentyl glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified diacrylate, etc. are mentioned.

As such a trifunctional or more than trifunctional monomer, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, ethylene isocyanurate Oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, Caprolactone modified pentaerythritol tetra(meth)acrylate, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaeryth Ritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, ethoxylated 15 glycerin triacrylate, etc. are mentioned.

Moreover, the Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can also be used together, As a Michael adduct of such acrylic acid, (meth)acrylic acid dimer, (meth)acrylic acid trimer, (meth)acrylic acid A tetramer etc. are mentioned. As said 2-acryloyloxyethyl dicarboxylic acid monoester, it is carboxylic acid which has a specific substituent, For example, 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrofu A deoxidized monoester etc. are mentioned. Moreover, other oligoester acrylates etc. are mentioned.

In the invention according to the first and second aspects of the present invention, the content of ethylenically unsaturated monomers other than urethane (meth)acrylate is 60% by weight or less among the precurable components contained in the active energy ray-curable resin composition. It is preferred, particularly preferably 55% by weight or less, more preferably 50% by weight or less. In addition, as a lower limit, it is 5 weight% normally.

On the other hand, in the invention according to the third aspect of the present invention, the content of ethylenically unsaturated monomers other than urethane (meth)acrylate is preferably 50% by weight or less among the precurable components contained in the active energy ray-curable resin composition. and particularly preferably 40% by weight or less, more preferably 30% by weight or less, particularly preferably 20% by weight or less. In addition, as a lower limit, it is 5 weight% normally.

As said surface conditioning agent, a cellulose resin, an alkyd resin, etc. are mentioned, for example. Such a cellulose resin has an effect of improving the surface smoothness of the coating film, and the alkyd resin has an effect of imparting film formability at the time of application. These can be used individually or in combination of 2 or more types.

As the labeling agent, a known general labeling agent can be used as long as it has an action of imparting wettability to the substrate of the coating solution and lowering the surface tension, for example, silicone-modified resin, fluorine-modified resin, alkyl-modified resin, etc. can be used These can be used individually or in combination of 2 or more types.

As said polymerization inhibitor, the same thing as that used at the time of reaction can be used, For example, p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2, quinones such as 5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and mono-t-butylhydroquinone; 4-methoxyphenol; 2,6-di-t-butylcresol; Aromatics, p-t- butylcatechol, etc. are mentioned. These can be used individually or in combination of 2 or more types.

Moreover, in order that the active-energy-ray-curable resin composition of this invention may make the viscosity at the time of coating into an appropriate thing as needed, it is also preferable to use the organic solvent for dilution. Examples of such an organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, and ethyl cellosolve. and cellosolves such as cellosolves, aromatics such as toluene and xylene, glycol ethers such as propylene glycol monomethyl ether, acetate esters such as methyl acetate, ethyl acetate, and butyl acetate, and diacetone alcohol. These said organic solvents may be used independently and may use 2 or more types together.

When using two or more types together, a combination of glycol ethers such as propylene glycol monomethyl ether and ketones such as methyl ethyl ketone and alcohols such as methanol, ketones such as methyl ethyl ketone and alcohols such as methanol It is preferable from the viewpoint of the appearance of the coating film to select and use two or more types from a combination of alcohols such as methanol and the like.

The active energy ray-curable resin composition of this invention is used effectively as a curable composition for coating-film formation, such as an overcoat agent to various base materials, and an anchor coat agent. And after coating an active energy ray-curable resin composition to a base material (when the resin composition diluted with the organic solvent is coated, after drying again), it hardens|cures by irradiating an active energy ray.

As the base material to be coated with the active energy ray-curable resin composition of the present invention, for example, polyolefin-based resin, polyester-based resin, polycarbonate-based resin, acrylonitrile-butadienestyrene copolymer (ABS), polystyrene-based resin, etc. or plastic substrates such as these molded articles (films, sheets, cups, etc.), optical films such as polyethylene terephthalate film, triacetyl cellulose film, and cycloolefin film, these composite substrates, or glass fibers or inorganic materials mixed with the above materials metal (aluminum, copper, iron, SUS, zinc, magnesium, these alloys, etc.), glass, such as a composite base material, or the base material which provided the primer layer on these base materials, etc. are mentioned.

Examples of the coating method of the active energy ray-curable resin composition of the present invention include a wet coating method such as spray, shower, gravure, dipping, roll, spin, screen printing, etc., and is usually coated on a substrate at room temperature good to do

Moreover, the active-energy-ray-curable resin composition of this invention may be coated as it is, and it may dilute with an organic solvent and may apply. In the case of dilution, the organic solvent is used to dilute so that the solid content concentration is usually 3 to 70 wt%, preferably 5 to 60 wt%.

As drying conditions when dilution with the organic solvent is carried out, the temperature is usually 40 to 120°C, preferably 50 to 100°C, and the drying time is usually 1 to 20 minutes, preferably 2 to 10 minutes. .

At the time of coating the active energy ray-curable resin composition of this invention, it is preferable that the viscosity in 20 degreeC of a resin composition is 5-50,000 mPa*s, Especially preferably, it is 10-10,000 mPa*s, More preferably, 50 -5,000 mPa·s. If such a viscosity is outside the said range, there exists a tendency for coatability to fall.

In addition, the measuring method of the said viscosity at 20 degreeC is with a B-type viscometer. However, since it is a high viscosity in the state without solvent dilution, when the measurement by the B-type viscometer at 20 degreeC cannot be performed, it measures using the E-type viscometer at 60 degreeC.

As an active energy ray used when hardening the active energy ray-curable resin composition coated on the base material, For example, light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X rays, electromagnetic waves such as γ rays, Although an electron beam, a proton beam, a neutron beam, etc. can be used, hardening by ultraviolet irradiation is advantageous from a hardening rate, the easiness of acquisition of an irradiation apparatus, price, etc. In addition, when electron beam irradiation is performed, even if it does not use a photoinitiator (D), it can harden|cure.

When curing by UV irradiation, high-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, metal halide camps, xenon lamps, chemical lamps, electrodeless discharge lamps, LED lamps, etc. Usually 30 to 3,000 mJ/cm 2 , preferably 100 to 1,500 mJ/cm 2 can be irradiated with ultraviolet rays.

After ultraviolet irradiation, if necessary, it can heat and can also aim at perfection of hardening.

As a coating film thickness (film thickness after hardening), it is 1-1,000 micrometers in consideration of light transmission so that a photoinitiator (D) may react uniformly as an active energy ray-curable coating film normally, Preferably it is 2-500 micrometers. and particularly preferably 3 to 200 µm.

It is preferable to use the active energy ray-curable resin composition of this invention as a coating agent, and it is preferable to use especially as a coating agent for hard-coats, and a coating agent for optical films.

In the present invention, the active energy ray-curable resin composition is coated on a polyethylene terephthalate (PET) film having a size of 15 cm x 15 cm and a thickness of 100 μm so that the cured coating film has a thickness of 10 μm, and the temperature is 60° C. for 3 minutes. After drying, a high-pressure mercury lamp of 80 W is prepared at a height of 18 cm from the PET film surface, and ultraviolet rays are irradiated at a speed of 5.1 m/min so that the cumulative irradiation amount is 500 mJ/cm 2 , whereby a cured coating film can be obtained. The cured coating film is cut to be 10 cm × 10 cm, and the average value of the protruding heights of the four corners of the cut cured coating film is 40 mm or less, particularly 30 mm or less, and 25 mm or less It is preferable to use as a coating agent to become a cured coating film.

In addition, in the present invention, the active energy ray-curable resin composition is coated on an easy-adhesive PET film having a size of 15 cm × 15 cm and a thickness of 125 μm so that the cured coating film has a thickness of 10 μm, and after drying at a temperature of 60° C. for 3 minutes, A cured coating film can be obtained by preparing an 80 W high-pressure mercury lamp at a height of 18 cm from the surface of the easily-adhesive PET film and irradiating with ultraviolet rays at a rate of 5.1 m/min so that the cumulative irradiation amount is 500 mJ/cm 2 . The cured coating film was evaluated for flexibility using a cylindrical mandrel bending tester in accordance with JIS K 5600-5-1, and the maximum diameter (integer) at which cracking or peeling occurs when the cured coating film for evaluation is wound around a test rod. value, mm) is preferably 20 mm or less, in particular 15 mm or less, more preferably 10 mm or less, especially 8 mm or less.

And, in the present invention, the active energy ray-curable resin composition is coated on an easily adhesive PET film having a size of 15 cm × 15 cm and a thickness of 125 μm so that the cured coating film has a thickness of 10 μm, and after drying at a temperature of 60° C. for 3 minutes, A cured coating film can be obtained by preparing an 80 W high-pressure mercury lamp at a height of 18 cm from the surface of the easily-adhesive PET film and irradiating with ultraviolet rays at a rate of 5.1 m/min so that the cumulative irradiation amount is 500 mJ/cm 2 . In the cured coating film, steel wool (manufactured by Nippon Steel Wool Co., Ltd., Bonstar #0000) was used and the surface of the cured coating film was reciprocated 10 times while applying a load of 500 g. It is preferable that there are no scratches.

The invention according to the first aspect of the present invention is a (meth)acrylate (a1) in a mixture (A) of the above (meth)acrylates (a1) to (a4), which are reactants of pentaerythritol and (meth)acrylic acid. ) to (a3) and urethane (meth)acrylate-based composition [I] in which polyvalent isocyanate (CA) reacted, and the hydroxyl group of the mixture (A) is 200 mgKOH/g or more It is an active energy ray-curable resin composition . Since this active energy ray-curable resin composition has small cure shrinkage, it is hard to curl, and can form a cured coating film excellent in hardness and flexibility, and also. Even if it is a coating film in an uncured state before curing, the surface of the coating film does not stick, and it has the effect of forming a coating film surface that is tack-free. It is useful also as a paint, ink, etc.

The invention according to the second aspect of the present invention is a (meth)acrylate (a1) in a mixture (A) of the above (meth)acrylates (a1) to (a4) which is a reaction product of pentaerythritol and (meth)acrylic acid. ) to (a3) and urethane (meth)acrylate-based composition [I] in which polyvalent isocyanate (CA) reacted, and the following (meth)acrylate (b1) which is a reaction product of dipentaerythritol and (meth)acrylic acid ) to (b6) containing a urethane (meth)acrylate-based composition [II] in which (meth)acrylates (b1) to (b5) and polyvalent isocyanate (CB) in the mixture (B) are reacted, the mixture ( It is an active energy ray-curable resin composition in which the hydroxyl value of A) is 200 mgKOH/g or more, and the hydroxyl value of the said mixture (B) is 40 mgKOH/g or more. Since this active energy ray-curable resin composition has a small cure shrinkage, it is difficult to curl and has the effect of forming a cured coating film excellent in hardness and flexibility, and is particularly useful as a coating agent (also a coating agent for a hard coat or a coating agent for an optical film) Moreover, it is useful also as a paint, an ink, etc.

The invention according to the third aspect of the present invention provides (meth)acrylates (a1) to (a3) in [α], (meth)acrylates (b1) to (b5) in [β], and It is an active energy ray-curable resin composition containing the urethane (meth)acrylate type composition [III] which polyhydric isocyanate (CC) reacted. Since this active energy ray-curable resin composition has a small cure shrinkage, it is difficult to curl, and has the effect of forming a cured coating film excellent in hardness, flexibility and scratch resistance, especially as a coating agent (for a coating agent for a hard coat or for an optical film) coating agent). Moreover, it is useful also as a paint, ink, etc.

Example

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded. In addition, in the Example, "part" and "%" mean a weight basis.

<<Example using urethane (meth)acrylate-based composition [I]>>

Urethane acrylate-based composition [I] ([I-1] to [I-4]) as follows, and urethane acrylate-based composition [I'] ([I'-1] to [I'-] for comparison 4]) was prepared.

[Preparation of urethane acrylate-based composition [I-1]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 36 g of isophorone diisocyanate (C-1) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (of pentaerythritol acrylic acid adduct) 64 g, ethyl acetate 100 g as a solvent, 4-methoxyphenol 0.08 g as a polymerization inhibitor, and 0.05 g dibutyltin dilaurate as a reaction catalyst, reacted at 60° C. to reduce 0.1% of the remaining isocyanate groups When the reaction was completed, the urethane acrylate-based composition [I-1] was obtained (resin content concentration of 50%).

The weight average molecular weight of the obtained urethane acrylate type composition [I-1] was 4,700, and the viscosity in 20 degreeC was 80 mPa*s. In addition, the measurement of the viscosity in 20 degreeC was implemented using the B-type viscometer. The viscosity measurement in 20 degreeC is as follows.

In addition, the content rate of each component with respect to the sum total of the following components (a1) - (a4) in an acrylate mixture (A-1) is as follows.

(a1) pentaerythritol monoacrylate 4%

(a2) pentaerythritol diacrylate 29%

(a3) pentaerythritol triacrylate 49%

(a4) pentaerythritol tetraacrylate 18%

In addition, the content rate of each component in a mixture is measured by using a column (made by Imtakt, Cadenza CD-C18100 x 3 mm 3 micrometers) for a liquid chromatograph (manufactured by Agilent, "Technology HP 1100").

[Preparation of urethane acrylate-based composition [I-2]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 33 g of hydrogenated xylene diisocyanate (C-2) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (Pentaeryth) 67 g of acrylic acid adduct of ritol), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added, reacted at 60° C., and the remaining isocyanate group was 0.1 %, the reaction was terminated, and a urethane acrylate-based composition [I-2] was obtained (resin content concentration of 50%).

The weight average molecular weight of the obtained urethane acrylate type composition [I-2] was 6,200, and the viscosity in 20 degreeC was 65 mPa*s.

[Preparation of urethane acrylate-based composition [I-3]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 43 g of tolylene diisocyanate (C-3) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (pentaerythritol) 97 g of acrylic acid adduct), 60 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst, reacted at 60° C., and the remaining isocyanate group is 0.1% The reaction was terminated at the time of addition, and a urethane acrylate-based composition [I-3] was obtained (resin content concentration of 70%).

The weight average molecular weight of the obtained urethane acrylate type composition [I-3] was 7, 300, and the viscosity in 20 degreeC was 161,000 mPa*s.

[Preparation of urethane acrylate-based composition [I-4]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 48 g of xylene diisocyanate (C-4) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (acrylic acid of pentaerythritol) 90 g of adduct), 60 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60° C. to obtain 0.1% of the remaining isocyanate groups. At this point, the reaction was terminated to obtain a urethane acrylate-based composition [I-4] (resin content concentration of 70%).

As for the weight average molecular weight of the obtained urethane acrylate type composition [I-4], since the viscosity in 12,000 and 20 degreeC was high viscosity, it did not measure.

[Preparation of urethane acrylate-based composition [I'-1]]

In a flask equipped with a thermometer, a stirrer, a water cooling condenser, and a nitrogen gas inlet, 38.4 g of isophorone diisocyanate (C-1) and an acrylate mixture (A'-1) having a hydroxyl value of 120 mgKOH/g (of pentaerythritol) 161.6 g of acrylic acid adduct), 0.01 g of hydroquinone methyl ether as a polymerization inhibitor, and 0.01 g of dibutyltin dilaurate as a reaction catalyst, were left at 60° C. for 8 hours, and the residual isocyanate group was 0.3% or less. At this point, the reaction was terminated to obtain a urethane acrylate-based composition [I'-1] (resin content concentration of 100%).

The weight average molecular weight of the obtained urethane acrylate type composition [I'-1] was 1,400, and the viscosity in 60 degreeC was 3,000 mPa*s. However, since it was high viscosity, it measured using the E-type viscometer.

In addition, the content rate of each component with respect to the sum total of the following components (a1) - (a4) in an acrylate mixture (A'-1) is as follows.

(a2) pentaerythritol diacrylate 5%

(a3) pentaerythritol triacrylate 50%

(a4) pentaerythritol tetraacrylate 45%

However, regarding (a1) pentaerythritol monoacrylate, since content was below the measurement limit, the content rate of (a2)-(a4) component was shown.

[Preparation of urethane acrylate-based composition [I'-2]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 37 g of isophorone diisocyanate (C-1) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (pentaerythritol) of acrylic acid adduct) 14 g, polyester polyol consisting of adipic acid and neopentyl glycol (manufactured by DIC, "ODX-2044", number average molecular weight: about 2,000) 114 g, 4-methoxyphenol as a polymerization inhibitor 0.08 g, 0.05 g of dibutyltin dilaurate as a reaction catalyst was added and reacted at 60°C. When the remaining isocyanate groups became 3.9%, an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (acrylic acid of pentaerythritol) 35 g of adduct) was added, and it was made to react at 60 degreeC again. When the remaining isocyanate groups became 0.1%, the reaction was terminated to obtain a urethane acrylate-based composition [I'-2] (resin content concentration of 100%).

In addition, according to the said procedure, there is no reactant of only (A-1) and (C-1) in the obtained urethane acrylate type composition [I'-2].

The weight average molecular weight of the obtained urethane acrylate type composition [I'-2] was 18,000, and the viscosity in 60 degreeC was 700,000 mPa*s. However, since it was high viscosity, it measured using the E-type viscometer.

[Preparation of urethane acrylate-based composition [I'-3]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 25.8 g of isophorone diisocyanate (C-1) and an acrylate mixture (A'-2) having a hydroxyl value of 184.2 mgKOH/g (pentae 74.2 g of acrylic acid adduct of rythritol), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added, reacted at 60° C., and residual isocyanate When the group reached 0.1%, the reaction was terminated to obtain a urethane acrylate-based composition [I'-3] (resin content concentration of 50%).

The weight average molecular weight of the obtained urethane acrylate type composition [I'-3] was 2,100, and the viscosity in 20 degreeC was 73 mPa*s.

In addition, the content rate of each component with respect to the sum total of the following components (a1) - (a4) in an acrylate mixture (A'-2) is as follows.

(a1) pentaerythritol monoacrylate 1.6%

(a2) pentaerythritol diacrylate 14.6%

(a3) pentaerythritol triacrylate 49.6%

(a4) pentaerythritol tetraacrylate 34.2%

[Preparation of urethane acrylate-based composition [I'-4]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 23.3 g of hydrogenated xylene diisocyanate (C-2), an acrylate mixture (A'-2) having a hydroxyl value of 184.2 mgKOH/g ( 76.7 g of acrylic acid adduct of pentaerythritol), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst, and reacted at 60 ° C. When the remaining isocyanate groups became 0.1%, the reaction was terminated to obtain a urethane acrylate-based composition [I'-4] (resin content concentration of 50%).

The weight average molecular weight of the obtained urethane acrylate type composition [I'-4] was 2, 200, and the viscosity in 20 degreeC was 85 mPa*s.

<Examples 1-4, Comparative Examples 1-4>

[Preparation of active energy ray-curable resin composition]

To the urethane acrylate composition ([I], [I']) obtained above, 1-hydroxycyclohexylphenyl ketone (manufactured by IGM, "Omnirad 184") as a photoinitiator (D) was added to 100 parts of a curing component 4 parts were mix|blended with respect to this, and the active energy ray-curable resin composition was obtained.

In Examples 3 and 4 and Comparative Examples 1 and 2, except that the obtained urethane acrylate composition ([I], [I']) was diluted with ethyl acetate so as to have a resin content of 50%, the above Thus, an active energy ray-curable resin composition was obtained.

About the obtained active energy ray-curable resin composition, the coating film (dry coating film) before hardening was formed as follows, and adhesion of the coating film was evaluated. In addition, a cured coating film was formed as follows, and the hardness and flexibility of the cured coating film were evaluated. The evaluation results are shown in Table 1 below.

[Sticking of dry coating film]

The active energy ray-curable resin composition obtained above was applied to a reverse-adhesive PET film (manufactured by Toyobo, "A4300", size 15 cm × 15 cm, thickness 125 µm) on a substrate using a bar coater, and the cured coating film was 10 µm It coated so that it might become thick, and it dried at 60 degreeC for 3 minute(s). The obtained coating film before curing was subjected to a probe tack test using a tacking tester (manufactured by Lesca, “TAC-II”) under the conditions of a press-in speed of 120 mm/min, a lifting speed of 600 mm/min, a pressure of 20.4 gf, and a pressurization time of 1.0 second. carried out.

[Hardness of cured coating film]

The active energy ray-curable resin composition obtained above is applied onto a substrate of an easily-adhesive PET film (manufactured by Toyobo, "A4300", size 15 cm × 15 cm, thickness 125 µm) using a bar coater so that the cured coating film has a thickness of 10 µm. After drying at 60° C. for 3 minutes, using a high-pressure mercury lamp 80 W, 1 lamp, 2 passes of ultraviolet irradiation (accumulated irradiation amount 500 mJ/cm 2 ) from a height of 18 cm at a conveyor speed of 5.1 m/min were performed, and a cured coating film has formed About the said cured coating film coated on the easily adhesive PET film, according to JISK-5600, the test was done and pencil hardness was measured.

[Flexibility of cured coating film]

A cured coating film was formed in the same manner as in the above hardness evaluation, and the cured coating film coated on the easily adhesive PET film was evaluated for flexibility in accordance with JIS K 5600-5-1 using a cylindrical mandrel bending tester. When the cured coating film for evaluation was wound around a test rod so that the coating film surface turned outward, the maximum diameter (integer value, mm) at which cracks or peeling occurred was measured. It means that it is a coating film with high flexibility, so that a value is small.

From the above evaluation results, the cured coating film obtained from the active energy ray-curable resin composition containing the urethane acrylate-based composition [I] of Examples 1 to 4 is not only excellent in hardness and flexibility, but also different from the coating film in an uncured state before curing. It can be seen that there is no adhesion.

On the other hand, in Comparative Example 1 using a urethane acrylate-based composition other than the specific urethane acrylate-based composition [I], Comparative Example 1 was inferior in flexibility of the cured coating film, and the coating film before curing had adhesion. Moreover, in Comparative Example 2, the hardness of a cured coating film was inferior, and the coating film before hardening had sticking. In Comparative Examples 3 and 4, the flexibility of the cured coating film was inferior.

From these, it can be seen that the active energy ray-curable resin compositions of Examples 1 to 4 are tack-free, have good hardness and flexibility, and are useful for coatings and the like, especially for hard coat coatings and optical film coatings. have.

<<Examples using urethane (meth)acrylate-based compositions [I] and [II]>>

Urethane acrylate-based compositions [I] ([I-5] to [I-7]), [II] ([II-1] to [II-2]) as follows, and urethane acrylate-based compositions for comparison Compositions [I'] ([I'-5] to [I'-7]) were prepared.

[Urethane acrylate-based composition [I-5]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 36 g of isophorone diisocyanate (C-1) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (of pentaerythritol acrylic acid adduct) 64 g, ethyl acetate 100 g as a solvent, 0.08 g 4-methoxyphenol as a polymerization inhibitor, 0.05 g dibutyltin dilaurate as a reaction catalyst, and reacted at 60° C. to reduce the residual isocyanate group by 0.1% At this point, the reaction was terminated, and a urethane acrylate-based composition [I-5] was obtained (resin content concentration of 50%).

The weight average molecular weight of the obtained urethane acrylate type composition [I-5] was 4,700, and the viscosity in 20 degreeC was 80 mPa*s. In addition, the measurement of the viscosity in 20 degreeC was implemented using the B-type viscometer. The viscosity measurement in 20 degreeC is as follows.

In addition, the content rate of each component with respect to the sum total of the following components (a1) - (a4) in an acrylate mixture (A-1) is as follows.

(a1) pentaerythritol monoacrylate 4%

(a2) pentaerythritol diacrylate 29%

(a3) pentaerythritol triacrylate 49%

(a4) pentaerythritol tetraacrylate 18%

[Preparation of urethane acrylate-based composition [I-6]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 33 g of hydrogenated xylene diisocyanate (C-2) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (Pentaeryth) 67 g of acrylic acid adduct of ritol), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added, reacted at 60° C., and the residual isocyanate group was 0.1 %, the reaction was terminated to obtain a urethane acrylate-based composition [I-6] (resin content concentration of 50%).

The weight average molecular weight of the obtained urethane acrylate composition [I-6] was 6,200, and the viscosity in 20 degreeC was 65 mPa*s.

[Preparation of urethane acrylate-based composition [I-7]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 32 g of xylene diisocyanate (C-4) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (of pentaerythritol acrylic acid adduct) 68 g, ethyl acetate 100 g as a solvent, 0.08 g 4-methoxyphenol as a polymerization inhibitor, 0.05 g dibutyltin dilaurate as a reaction catalyst, and reacted at 60° C. At this point, the reaction was terminated, and a urethane acrylate-based composition [I-7] was obtained (resin content concentration of 50%).

The weight average molecular weight of the obtained urethane acrylate type composition [I-7] was 5,900, and the viscosity in 20 degreeC was 50 mPa*s.

[Preparation of urethane acrylate-based composition [II-1]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 27.9 g of hydrogenated xylene diisocyanate (C-2) and an acrylate mixture (B-1) having a hydroxyl value of 96 mgKOH/g (di Addition product of acrylic acid to pentaerythritol) 172.1 g, 4-methoxyphenol 0.08 g as a polymerization inhibitor, and 0.1 g dibutyltin dilaurate as a reaction catalyst were added, and reacted at 60° C. to reduce the residual isocyanate group by 0.1%. When the reaction was completed, the urethane acrylate-based composition [II-1] was obtained (resin content concentration of 100%).

The weight average molecular weight of the obtained urethane acrylate type composition [II-1] was 5,500, and the viscosity in 60 degreeC was 39,400 mPa*s. In addition, the measurement of the viscosity in 60 degreeC was implemented using the E-type viscometer. The viscosity measurement in 60 degreeC is as follows.

In addition, the content rate of each component with respect to the sum total of the following components (b1) - (b6) in an acrylate mixture (B-1) is as follows.

(b4) dipentaerythritol tetraacrylate 18%

(b5) dipentaerythritol pentaacrylate 51%

(b6) dipentaerythritol hexaacrylate 31%

However, regarding (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate, since the content was below the measurement limit, (b4) ) to (b6) components were shown.

[Preparation of urethane acrylate-based composition [II-2]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 31.3 g of isophorone diisocyanate (C-1), an acrylate mixture (B-1) having a hydroxyl value of 96 mgKOH/g (dipentae Acrylic acid adduct of rithritol) 168.7 g, 4-methoxyphenol 0.08 g as a polymerization inhibitor, and 0.1 g dibutyltin dilaurate as a reaction catalyst were added, reacted at 60° C., when the remaining isocyanate groups became 0.1% After completing the reaction, a urethane acrylate-based composition [II-2] was obtained (resin content concentration of 100%). The weight average molecular weight of the obtained urethane acrylate type composition [II-2] was 67,000, and the viscosity in 60 degreeC was 65,000 mPa*s.

[Preparation of urethane acrylate-based composition [II-3]]

In a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 13.2 g of isophorone diisocyanate (C-1) and an acrylate mixture (B-2) having a hydroxyl value of 50 mgKOH/g (dipentaeryth) 186.8 g of acrylic acid adduct of ritol), 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added, reacted at 60° C., when the remaining isocyanate groups became 0.1% After completion of the reaction, a urethane acrylate-based composition [II-3] was obtained (resin content concentration of 100%).

The weight average molecular weight of the obtained urethane acrylate type composition [II-3] was 2,000, and the viscosity in 60 degreeC was 1,700 mPa*s.

In addition, the content rate of each component with respect to the sum total of the following components (b1) - (b6) in an acrylate mixture (B-2) is as follows.

(b4) dipentaerythritol tetraacrylate 6%

(b5) dipentaerythritol pentaacrylate 54%

(b6) 40% dipentaerythritol hexaacrylate

However, regarding (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate, since the content was below the measurement limit, (b4) ) to (b6) components were shown.

[Preparation of urethane acrylate-based composition [I'-5]]

In a flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 38.4 g of isophorone diisocyanate (C-1) and an acrylate mixture (A'-1) having a hydroxyl value of 118 mgKOH/g (of pentaerythritol 161.6 g of acrylic acid adduct), 0.01 g of hydroquinone methyl ether as a polymerization inhibitor, and 0.01 g of dibutyltin dilaurate as a reaction catalyst, reacted at 60° C. for 8 hours, and the residual isocyanate group was 0.3% or less At this point, the reaction was terminated to obtain a urethane acrylate-based composition [I'-5] (resin content concentration of 100%).

The weight average molecular weight of the obtained urethane acrylate type composition [I'-5] was 1,400, and the viscosity in 60 degreeC was 3,000 mPa*s.

In addition, the content rate of each component with respect to the sum total of the following components (a1) - (a4) in an acrylate mixture (A'-1) is as follows.

(a2) pentaerythritol diacrylate 5%

(a3) pentaerythritol triacrylate 50%

(a4) pentaerythritol tetraacrylate 45%

However, regarding (a1) pentaerythritol monoacrylate, since content was below the measurement limit, the content rate of (a2)-(a4) component was shown.

[Preparation of urethane acrylate-based composition [I'-6]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 23.3 g of hydrogenated xylene diisocyanate (C-2), an acrylate mixture (A'-2) having a hydroxyl value of 184.2 mgKOH/g ( 76.7 g of acrylic acid adduct of pentaerythritol), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst, and reacted at 60 ° C. When the remaining isocyanate groups became 0.1%, the reaction was terminated to obtain a urethane acrylate-based composition [I'-6] (resin content concentration of 50%). The weight average molecular weight of the obtained urethane acrylate type composition [I'-6] was 2,200, and the viscosity in 20 degreeC was 85 mPa*s.

In addition, the content rate of each component with respect to the sum total of the following components (a1) - (a4) in an acrylate mixture (A'-2) is as follows.

(a1) pentaerythritol monoacrylate 1.6%

(a2) pentaerythritol diacrylate 14.6%

(a3) pentaerythritol triacrylate 49.6%

(a4) pentaerythritol tetraacrylate 34.2%

[Preparation of urethane acrylate-based composition [I'-7]]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 25.8 g of isophorone diisocyanate (C-1) and an acrylate mixture (A'-2) having a hydroxyl value of 184.2 mgKOH/g (pentae 74.2 g of acrylic acid adduct of rythritol), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added, reacted at 60° C., and residual isocyanate When the group reached 0.1%, the reaction was terminated to obtain a urethane acrylate-based composition [I'-7] (resin content concentration of 50%).

The weight average molecular weight of the obtained urethane acrylate type composition [I'-7] was 2,100, and the viscosity in 20 degreeC was 73 mPa*s.

<Examples 5-12, Comparative Examples 5-9>

[Preparation of active energy ray-curable resin composition]

The urethane acrylate-based compositions ([I], [II], and [I']) obtained above have a formulation composition as shown in Table 2 below, and 1-hydroxycyclohexylphenylketone (D) as a photopolymerization initiator (D). The IGM company make, "Omnirad 184") was mix|blended 4 parts with respect to 100 parts of hardening components, and the energy-beam curable resin composition was obtained.

About the obtained active energy ray-curable resin composition, the cured coating film was formed as follows, and the hardness and flexibility of the cured coating film were evaluated. The evaluation results are shown in Table 2 below.

[Hardness of cured coating film]

The active energy ray-curable resin composition obtained above was applied to an easily adhesive PET film (manufactured by Toyobo Co., Ltd., "A4300", size 15 cm × 15 cm, thickness 125 μm) on a substrate using a bar coater so that the cured coating film had a thickness of 10 μm. After coating and drying at 60° C. for 3 minutes, 2 passes of UV irradiation (accumulated irradiation amount 500 mJ/cm 2 ) was performed from a height of 18 cm using a high-pressure mercury lamp 80 W and 1 lamp at a conveyor speed of 5.1 m/min to make a cured coating film formed About the said cured coating film coated on the easily adhesive PET film, according to JISK-5600, the test was done and pencil hardness was measured.

[Flexibility of cured coating film]

A cured coating film was formed in the same manner as in the above hardness evaluation, and the cured coating film coated on the easily adhesive PET film was evaluated for flexibility in accordance with JIS K 5600-5-1 using a cylindrical mandrel bending tester. When the cured coating film for evaluation was wound around a test rod so that the coating film surface turned outward, the maximum diameter (integer value, mm) at which cracks or peeling occurred was measured. It means that it is a coating film with high flexibility, so that a value is small.

From the above evaluation results, it can be seen that the cured coating films obtained from the active energy ray-curable resin compositions containing the urethane acrylate-based compositions [I] and [II] of Examples 5 to 12 are excellent in both hardness and flexibility. have. On the other hand, in Comparative Example 5 using only the urethane acrylate composition [II] without containing the urethane acrylate composition [I], the flexibility of the cured coating film was inferior. Moreover, also about the comparative examples 6 and 7 containing the urethane acrylate type composition prepared using the acrylate mixture with a low hydroxyl value, the flexibility of a cured coating film was inferior.

Moreover, also about the comparative examples 8 and 9 containing the prepared urethane acrylate type composition using the acrylate mixture with a slightly high hydroxyl value, the flexibility of a cured coating film was inferior.

From this, it turns out that the active-energy-ray-curable resin composition of the said Examples 5-12 has favorable hardness and flexibility, and is useful about the use of a coating agent etc., especially the coating agent for hard-coats, and the coating agent for optical films.

<<Example using urethane (meth)acrylate composition [III]>>

Prior to the preparation of the urethane (meth) acrylate-based composition, a mixture (A), a mixture (A') (for comparative examples), a mixture (B), a polyvalent isocyanate (C), and a photopolymerization initiator (D) were prepared as follows. .

[Mixture (A)]

-A-1: In the acrylic acid adduct of pentaerythritol with a hydroxyl value of 288 mgKOH/g, the content ratio of each component with respect to the sum total of components (a1)-(a4) as follows is as follows.

(a1) pentaerythritol monoacrylate 4%

(a2) pentaerythritol diacrylate 29%

(a3) pentaerythritol triacrylate 49%

(a4) pentaerythritol tetraacrylate 18%

[Mixture (A') (for comparative example)]

-A'-1: In the acrylic acid adduct of pentaerythritol with a hydroxyl value of 118 mgKOH/g, the content ratio of each component with respect to the sum total of following components (a1) - (a4) is as follows.

(a2) pentaerythritol diacrylate 5%

(a3) pentaerythritol triacrylate 50%

(a4) pentaerythritol tetraacrylate 45%

However, regarding (a1) pentaerythritol monoacrylate, since content was below the measurement limit, the content rate of (a2)-(a4) component was shown.

-A'-2: In the acrylic acid adduct of pentaerythritol with a hydroxyl value of 184.2 mgKOH/g, the content ratio of each component with respect to the sum total of following components (a1) - (a4) is as follows.

(a1) pentaerythritol monoacrylate 1.6%

(a2) pentaerythritol diacrylate 14.6%

(a3) pentaerythritol triacrylate 49.6%

(a4) pentaerythritol tetra acrylate 34.2%

[Mixture (B)]

-B-1: In the acrylic acid adduct of dipentaerythritol having a hydroxyl value of 96 mgKOH/g, the content ratio of each component with respect to the total of the following components (b1) to (b6) is as follows.

(b4) dipentaerythritol tetraacrylate 18%

(b5) dipentaerythritol pentaacrylate 51%

(b6) dipentaerythritol hexaacrylate 31%

However, regarding (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate, since the content was below the measurement limit, (b4) ) to (b6) components were shown.

-B-2: In the acrylic acid adduct of dipentaerythritol with a hydroxyl value of 54 mgKOH/g, the content ratio of each component with respect to the sum total of the following components (b1) - (b6) is as follows.

(b4) dipentaerythritol tetraacrylate 6%

(b5) dipentaerythritol pentaacrylate 54%

(b6) 40% dipentaerythritol hexaacrylate

However, regarding (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate, since the content was below the measurement limit, (b4) ) to (b6) components were shown.

[Polyvalent Isocyanate (C)]

C-1: isophorone diisocyanate

C-2: Hydrogenated xylene diisocyanate

C-4: xylene diisocyanate

[Photoinitiator (D)]

・D-1: 1-hydroxycyclohexylphenyl ketone (manufactured by IGM, "Omnirad 184")

[Synthesis Example 1: Urethane acrylate-based composition (III-1)]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 24 g of hydrogenated xylene diisocyanate (C-2) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (Pentaeryth) acrylic acid adduct of ritol) 33 g, acrylate mixture (B-1) having a hydroxyl value of 96 mgKOH/g (acrylic acid adduct of dipentaerythritol) 43 g, ethyl acetate 100 g as a solvent, 4-methoxyphenol as a polymerization inhibitor 0.08 g and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C. When the remaining isocyanate groups became 0.1%, the reaction was terminated to obtain a urethane acrylate-based composition (III-1) ( resin concentration 50%).

The weight average molecular weight of the obtained urethane acrylate type composition (III-1) was 4,900, and the viscosity in 20 degreeC was 40 mPa*s. In addition, the measurement of the viscosity in 20 degreeC was implemented using the B-type viscometer. The viscosity measurement in 20 degreeC is as follows.

[Synthesis Example 2: Urethane acrylate-based composition (III-2)]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 23 g of xylene diisocyanate (C-4) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (pentaerythritol) of acrylic acid adduct) 33 g, an acrylate mixture (B-1) having a hydroxyl value of 96 mgKOH/g (acrylic acid adduct of dipentaerythritol) 44 g, ethyl acetate 100 g as a solvent, 4-methoxyphenol as a polymerization inhibitor 0.08 g and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added, reacted at 60° C., the reaction was terminated when the remaining isocyanate groups became 0.1%, and a urethane acrylate-based composition (III-2) was obtained ( resin concentration 50%).

The weight average molecular weight of the obtained urethane acrylate composition (III-2) was 4,600, and the viscosity in 20 degreeC was 30 mPa*s.

[Synthesis Example 3: Urethane acrylate-based composition (III-3)]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 24 g of hydrogenated xylene diisocyanate (C-2) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (Pentaeryth) acrylic acid adduct of ritol) 35 g, acrylate mixture (B-2) having a hydroxyl value of 54 mgKOH/g (acrylic acid adduct of dipentaerythritol) 81 g, ethyl acetate 60 g as a solvent, 4-methoxy as a polymerization inhibitor 0.08 g of phenol and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added, reacted at 60° C., the reaction was terminated when the remaining isocyanate groups became 0.1%, and a urethane acrylate-based composition (III-3) was obtained. (resin content 70%).

The weight average molecular weight of the obtained urethane acrylate composition (III-3) was 3,300, and the viscosity in 20 degreeC was 460 mPa*s.

[Synthesis Example 4: Urethane acrylate-based composition (III-4)]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 39 g of isophorone diisocyanate (C-1) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (of pentaerythritol acrylic acid adduct) 49 g, hydroxyl value 54 mgKOH/g acrylate mixture (B-2) (acrylic acid adduct of dipentaerythritol) 112 g, 4-methoxyphenol 0.08 g as a polymerization inhibitor, di 0.05 g of butyltin dilaurate was added, and it was made to react at 60 degreeC, when the residual isocyanate group became 0.1%, the reaction was complete|finished, and the urethane acrylate type composition (III-3) was obtained (resin content concentration 100%).

The weight average molecular weight of the obtained urethane acrylate composition (III-4) was 3,800. Since the viscosity was very high, the viscosity could not be measured.

[Synthesis Example 5: Urethane acrylate composition (III'-1)]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 22 g of hydrogenated xylene diisocyanate (C-2) and an acrylate mixture (A'-1) having a hydroxyl value of 118 mgKOH/g (pentae 78 g of acrylic acid adduct of rythritol), 40 g of an acrylate mixture (B-1) having a hydroxyl value of 96 mgKOH/g (acrylic acid adduct of dipentaerythritol), 60 g of ethyl acetate as a solvent, 4-methoxy as a polymerization inhibitor 0.08 g of phenol and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added, reacted at 60° C., the reaction was terminated when the remaining isocyanate groups became 0.1%, and a urethane acrylate-based composition (III′-1) was prepared obtained (resin content concentration of 70%).

The weight average molecular weight of the obtained urethane acrylate type composition (III'-1) was 1,700, and the viscosity in 20 degreeC was 140 mPa*s.

[Synthesis Example 6: Urethane acrylate-based composition (III'-2)]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 21.3 g of hydrogenated xylene diisocyanate (C-2), an acrylate mixture (A'-2) having a hydroxyl value of 184.2 mgKOH/g ( Acrylic acid adduct of pentaerythritol) 61.0 g, acrylate mixture (B-1) having a hydroxyl value of 96 mgKOH/g (acrylic acid adduct of dipentaerythritol) 17.6 g, ethyl acetate 100 g as a solvent, as a polymerization inhibitor 0.08 g of 4-methoxyphenol and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added, reacted at 60° C., the reaction was terminated when the remaining isocyanate groups became 0.1%, and the urethane acrylate-based composition (III' -2) was obtained (resin content concentration of 50%).

The weight average molecular weight of the obtained urethane acrylate type composition (III'-2) was 2,300, and the viscosity in 20 degreeC was 65 mPa*s.

[Synthesis Example 7: Urethane acrylate composition (III'-3)]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 32 g of xylene diisocyanate (C-4) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH/g (acrylic acid of pentaerythritol) Additive) 68 g, 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60° C. to obtain 0.1% of the remaining isocyanate groups. At this point, the reaction was terminated to obtain a urethane acrylate-based composition (III'-3) (resin content concentration of 50%).

The weight average molecular weight of the obtained urethane acrylate type composition (III'-3) was 5,900, and the viscosity in 20 degreeC was 50 mPa*s.

[Synthesis Example 8: Preparation of urethane acrylate-based composition (III'-4)]

In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 28 g of hydrogenated xylene diisocyanate (C-2) and an acrylate mixture (B-1) having a hydroxyl value of 96 mgKOH/g (dipenta 172 g of acrylic acid adduct of erythritol), 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst, reacted at 60° C., when the remaining isocyanate groups became 0.1% to terminate the reaction, and a urethane acrylate-based composition (III'-4) was obtained (resin content concentration of 100%).

The weight average molecular weight of the obtained urethane acrylate composition (III'-4) was 5,500, and the viscosity in 60 degreeC was 39,400 mPa*s. In addition, the measurement of the viscosity in 60 degreeC was implemented using the E-type viscometer.

<Examples 13-16, Comparative Examples 10-13>

[Active energy ray-curable resin composition]

To the urethane acrylate-based compositions (III-1 to 4, III'-1 to 4) obtained above, 1-hydroxycyclohexylphenyl ketone (manufactured by IGM, "Omnirad 184") as a photoinitiator (D) was added 4 parts were mix|blended with respect to 100 parts of hardening components, and the active energy ray-curable resin composition was obtained.

About the obtained active energy ray-curable resin composition, the cured coating film was formed as follows, and the hardness, flexibility, and abrasion resistance of the cured coating film were evaluated. The evaluation results are shown in Table 3 below.

[Hardness of cured coating film]

The active energy ray-curable resin composition obtained above was applied to an easily-adhesive PET film (manufactured by Toyobo, "A4300", size 15 cm × 15 cm, thickness 125 µm) on a substrate using a bar coater, and the cured coating film had a thickness of 10 µm. After drying at 60°C for 3 minutes, using a high-pressure mercury lamp 80W, 1 light, 2 passes of ultraviolet irradiation (accumulated irradiation amount 500 mJ/cm2) from a height of 18 cm at a conveyor speed of 5.1 m/min Thus, a cured coating film was formed.

About the said cured coating film coated on the easily adhesive PET film, according to JISK-5600, it tested and measured the pencil hardness.

[Flexibility of cured coating film]

A cured coating film was formed in the same manner as in the above hardness evaluation, and the cured coating film coated on the easily adhesive PET film was evaluated for flexibility in accordance with JIS K 5600-5-1 using a cylindrical mandrel bending tester. When the cured coating film for evaluation was wound around a test rod so that the coating film surface turned outward, the maximum diameter (integer value, mm) at which cracks or peeling occurred was measured. It means that it is a coating film with high flexibility, so that a value is small.

[Abrasion resistance of cured coating film]

A cured coating film was formed in the same manner as the hardness evaluation above, and the cured coating film coated on the easily adhesive PET film was cured while applying a load of 500 g using steel wool (manufactured by Nippon Steel Wool Co., Ltd., Bon Star #0000). After the surface of the coating film was made to reciprocate 10 times, the degree of damage to the surface was visually observed.

(evaluation)

○···Scratches cannot be identified

×···Scratches can be confirmed

It turns out that the cured coating film obtained from the active energy ray-curable resin composition containing the urethane acrylate type composition [III] of Examples 13-16 is excellent not only in hardness and flexibility but also in abrasion resistance from the said evaluation result.

On the other hand, in the case of Comparative Example 10 using the acrylic acid adduct (A'-1) of pentaerythritol having a low hydroxyl value of less than 200 mgKOH/g, in the mixtures (A) and (B), dipentaeryth In the case of Comparative Example 13 in which only the acrylic acid adduct (B-1) of ritol was used, the flexibility of the cured coating film was inferior. Moreover, in the case of Comparative Example 11 using the acrylic acid adduct (A'-2) of pentaerythritol with a slightly lower hydroxyl value, hardness was slightly inferior and abrasion resistance was inferior. Moreover, in the case of Comparative Example 12 using only the acrylic acid adduct (A-1) of pentaerythritol having a high hydroxyl value among mixtures (A) and (B), the scratch resistance of the cured coating film was inferior.

From these, it can be seen that the active energy ray-curable resin compositions of Examples 13 to 16 are excellent in abrasion resistance in addition to hardness and flexibility, and are useful for coating agents and the like, especially for coating agents for hard coats and coating agents for optical films. have.

About the said Example, although it showed about the specific form in this invention, the said Example is only a mere illustration and is not interpreted limitedly. Various modifications apparent to those skilled in the art are expected to fall within the scope of the present invention.

When the active energy ray-curable resin composition of the present invention forms a cured coating film, since curing shrinkage is small, it is difficult to curl, and a coating film excellent in hardness and flexibility can be formed. It is useful as a coating agent for Moreover, it is useful also as a paint, ink, etc. In addition, by pasting the resin composition side of the laminated film in an uncured state in which an active energy ray-curable resin composition layer is formed on a film to a molded article, and then performing active energy ray curing, a cured film can be easily formed on various molded articles. can

Claims (15)

(meth)acrylates (a1) to (a3) in a mixture (A) of the following (meth)acrylates (a1) to (a4) as a reaction product of pentaerythritol and (meth)acrylic acid, and polyvalent isocyanate (CA ) contains the reacted urethane (meth)acrylate-based composition [I],
The content ratio of pentaerythritol di(meth)acrylate (a2) in the mixture (A) of the (meth)acrylates (a1) to (a4) is 10 to 50% by weight,
The content ratio of pentaerythritol di(meth)acrylate (a2) to the total of the (meth)acrylates (a1) to (a3) is 15 to 55% by weight,
The hydroxyl value of the said mixture (A) is 200 mgKOH/g or more, The active energy ray-curable resin composition characterized by the above-mentioned.
(a1) pentaerythritol mono (meth) acrylate
(a2) pentaerythritol di(meth)acrylate
(a3) pentaerythritol tri (meth) acrylate
(a4) pentaerythritol tetra (meth) acrylate (meth)acrylates (a1) to (a3) in a mixture (A) of the following (meth)acrylates (a1) to (a4) as a reaction product of pentaerythritol and (meth)acrylic acid, and polyvalent isocyanate (CA ) reacted with a urethane (meth)acrylate-based composition [I], and a mixture (B) of the following (meth)acrylates (b1) to (b6), which are reactants of dipentaerythritol and (meth)acrylic acid Contains urethane (meth)acrylate-based composition [II] in which (meth)acrylates (b1) to (b5) and polyvalent isocyanate (CB) reacted;
The content ratio of pentaerythritol di(meth)acrylate (a2) in the mixture (A) of the (meth)acrylates (a1) to (a4) is 10 to 50% by weight,
The content ratio of pentaerythritol di(meth)acrylate (a2) to the total of the (meth)acrylates (a1) to (a3) is 15 to 55% by weight,
The hydroxyl value of the mixture (A) is 200 mgKOH/g or more, and the hydroxyl value of the mixture (B) is 40 mgKOH/g or more, The active energy ray-curable resin composition characterized by the above-mentioned.
Mixture (A)
(a1) pentaerythritol mono (meth) acrylate
(a2) pentaerythritol di(meth)acrylate
(a3) pentaerythritol tri (meth) acrylate
(a4) pentaerythritol tetra (meth) acrylate
mixture (B)
(b1) dipentaerythritol mono (meth) acrylate
(b2) dipentaerythritol di(meth)acrylate
(b3) dipentaerythritol tri(meth)acrylate
(b4) dipentaerythritol tetra(meth)acrylate
(b5) dipentaerythritol penta (meth) acrylate
(b6) dipentaerythritol hexa(meth)acrylate (meth)acrylates (a1) to (a3) in the following (meth)acrylates (a1) to (a4) mixture (A), which are reactants of pentaerythritol and (meth)acrylic acid, and dipentaerythritol (meth)acrylates (b1) to (b5) in the mixture (B) of the following (meth)acrylates (b1) to (b6), which are reactants of (meth)acrylic acid, and polyvalent isocyanate (CC) are reacted containing a urethane (meth)acrylate-based composition [III],
The content ratio of pentaerythritol di(meth)acrylate (a2) in the mixture (A) of the (meth)acrylates (a1) to (a4) is 10 to 50% by weight,
The content ratio of pentaerythritol di(meth)acrylate (a2) to the total of the (meth)acrylates (a1) to (a3) is 15 to 55% by weight,
Active energy ray-curable resin composition, characterized in that the hydroxyl value of the mixture (A) is 200 mgKOH/g or more, and the hydroxyl value of the mixture (B) is 40 mgKOH/g or more:
Mixture (A)
(a1) pentaerythritol mono (meth) acrylate
(a2) pentaerythritol di(meth)acrylate
(a3) pentaerythritol tri (meth) acrylate
(a4) pentaerythritol tetra (meth) acrylate
mixture (B)
(b1) dipentaerythritol mono (meth) acrylate
(b2) dipentaerythritol di(meth)acrylate
(b3) dipentaerythritol tri(meth)acrylate
(b4) dipentaerythritol tetra(meth)acrylate
(b5) dipentaerythritol penta (meth) acrylate
(b6) dipentaerythritol hexa(meth)acrylate. delete delete The method according to claim 1 or 2,
The weight average molecular weight of the said urethane (meth)acrylate type composition [I] is 1,000-20,000, The active energy ray-curable resin composition characterized by the above-mentioned. 4. The method of claim 2 or 3,
Active energy ray characterized in that the content of dipentaerythritol penta(meth)acrylate (b5) in the mixture (B) of the (meth)acrylates (b1) to (b6) is 15 to 60 wt% Curable resin composition. 4. The method of claim 2 or 3,
Active energy ray-curable resin characterized in that the content ratio of dipentaerythritol penta(meth)acrylate (b5) to the total of the (meth)acrylates (b1) to (b5) is 45 to 90% by weight. composition. 4. The method of claim 2 or 3,
Active energy ray characterized in that the content of dipentaerythritol tetra(meth)acrylate (b4) in the mixture (B) of the (meth)acrylates (b1) to (b6) is 1 to 35% by weight. Curable resin composition. 4. The method of claim 2 or 3,
Active energy ray-curable resin composition characterized in that the content ratio of dipentaerythritol tetra(meth)acrylate (b4) to the total of the (meth)acrylates (b1) to (b5) is 2 to 40% by weight. . 3. The method according to claim 2,
The weight average molecular weight of the said urethane (meth)acrylate type composition [II] is 1,000-20,000, The active energy ray-curable resin composition characterized by the above-mentioned. 4. The method of claim 3,
The weight average molecular weight of the said urethane (meth)acrylate type composition [III] is 1,000-20,000, The active energy ray-curable resin composition characterized by the above-mentioned. The active-energy-ray-curable resin composition of any one of Claims 1-3 is contained, The coating agent characterized by the above-mentioned. 14. The method of claim 13,
It is used as a coating agent for hard coats, The coating agent characterized by the above-mentioned. 14. The method of claim 13,
It is used as a coating agent for optical films, The coating agent characterized by the above-mentioned.