JP2017200984A - Urethane (meth) acrylate and curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide urethane (meth) acrylate that is obtained from polycarbonate diol as raw material, has excellent flexibility, and shows excellent wear resistance when used for coatings or moldings.SOLUTION: A urethane (meth) acrylate is a reaction product of an isocyanate compound having two or more isocyanate groups in one molecule, polycarbonate diol, and hydroxy group-containing (meth) acrylate having one or more (meth) acryloyl group in one molecule, wherein the polycarbonate diol has a structural unit represented by the following formula (1) and a terminal hydroxyl group, and the first structural unit contains a second structural unit of 20 mol% or more and 90 mol% or less with respect to the total amount of the first structural unit.SELECTED DRAWING: None

Description

  The present invention relates to a urethane (meth) acrylate and a curable composition.

  Many energy ray curable resins that have been cured by irradiation with ultraviolet rays and electron beams and thermosetting resins that are cured by heat have been developed and widely used in paints, inks, adhesives, adhesives, molding materials, etc. Yes. Among them, urethane (meth) acrylates are various types of urethanes (characteristics such as toughness, chemical resistance, flexibility, etc.) depending on the purpose because of the high degree of design freedom due to the variety of constituent materials. (Meth) acrylates can be produced.

  For example, urethane (meth) acrylate using polycarbonate diol as a raw material has various hydrolysis resistance, weather resistance, and chemical resistance as well as flexibility due to characteristics resulting from its structure. Many are introduced.

  For example, Patent Document 1 proposes a urethane (meth) acrylate using a polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol. Polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol is considered to be excellent in flexibility because it is amorphous.

  Patent Document 2 proposes a curable composition made of urethane (meth) acrylate made of polycarbonate diol made of 2-methyl-1,3-propanediol. This urethane (meth) acrylate composition is used for coating agents, adhesives, pressure-sensitive adhesives, etc., which have excellent physical properties such as chemical resistance, hydrolysis resistance, weather resistance, flexibility and adhesion. A polycarbonate diol composed of 2-methyl-1,3-propanediol is excellent in flexibility because it has lower crystallinity at room temperature than a conventional polycarbonate diol composed of 1,6-hexanediol. Further, since the concentration of carbonate groups in the polycarbonate diol is high, it is said to be excellent in chemical resistance and wear resistance.

JP 2005-171154 A JP 2008-37989 A

  However, the urethane (meth) acrylate disclosed in Patent Document 1 and Patent Document 2 is not always satisfactory with respect to various required physical properties. Specifically, the polycarbonate diol disclosed in Patent Document 1 may have a problem of deterioration in chemical resistance and wear resistance due to a low concentration of carbonate groups in the polycarbonate diol. Moreover, since the polycarbonate diol disclosed in Patent Document 2 has a methyl group in the side chain, its molecular mobility is inferior, its flexibility is insufficient, and its glass transition temperature is high, so that there is also a problem in low temperature characteristics There may be.

  Therefore, the present invention provides a urethane (meth) acrylate that is excellent in flexibility and has excellent wear resistance when used as a coating application or a molded article application, as obtained from polycarbonate diol as a raw material. Objective.

  As a result of earnest research to solve the above-mentioned problems of the prior art, the present inventor is excellent in flexibility by using a specific polycarbonate diol and a specific hydroxyl group-containing (meth) acrylate, and is used for coating or molding. As a result, the present inventors have found that it exhibits excellent wear resistance when used as the present invention.

（式中、Ｒ₁は、炭素数２〜２０である、二価の脂肪族炭化水素又は脂環族炭化水素を示す。）

［２］
前記ウレタン（メタ）アクリレートを加アルカリ加水分解して得られるモノマー混合物において、下記式（３）で表されるアリルアルコール化合物の含有量が、当該モノマー混合物の総量に対して、０．０１％以上、３．０％以下である、
［１］に記載のウレタン（メタ）アクリレート。
ＣＨ₂＝ＣＨ−Ｒ₂−ＯＨ （３）
（式中、Ｒ₂は、炭素数２〜２０である、二価の脂肪族炭化水素又は脂環族炭化水素を示す。）
［３］
前記ポリカーボネートジオールは、末端基の総量に対して、末端ビニル基を、０．３％以上５．０％以下含む、
［１］又は［２］に記載のウレタン（メタ）アクリレート。
［４］
前記ポリカーボネートジオールは、末端基の総量に対して、１級末端ヒドロキシル基を、９５．０％以上９９．５％以下含み、かつ、数平均分子量が、３００以上５０００以下である、
［１］〜［３］のいずれかに記載のウレタン（メタ）アクリレート。
［５］
前記イソシアネート化合物は、脂肪族ジイソシアネート化合物及び脂環族ジイソシアネート化合物からなる群より選択される１種又は２種以上である、
［１］〜［４］のいずれかに記載のウレタン（メタ）アクリレート。
［６］
［１］〜［５］のいずれかに記載のウレタン（メタ）アクリレートを含有する、
硬化性組成物。 That is, the present invention includes the following aspects.
[1]
It is a reaction product of an isocyanate compound having two or more isocyanate groups in one molecule, a polycarbonate diol, and a hydroxyl group-containing (meth) acrylate having one or more (meth) acryloyl groups in one molecule,
The polycarbonate diol has a structural unit represented by the following formula (1) and a terminal hydroxyl group,
The structural unit represented by the formula (1) contains 20 mol% or more and 90 mol% or less of the structural unit represented by the following formula (2) with respect to the total amount of the structural unit.
Urethane (meth) acrylate.

(In the formula, R ₁ represents a divalent aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 20 carbon atoms.)

[2]
In the monomer mixture obtained by alkali hydrolysis of the urethane (meth) acrylate, the content of the allyl alcohol compound represented by the following formula (3) is 0.01% or more with respect to the total amount of the monomer mixture. 3.0% or less,
The urethane (meth) acrylate according to [1].
_{CH 2 = CH-R 2 -OH} (3)
(In the formula, R ₂ represents a divalent aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 20 carbon atoms.)
[3]
The polycarbonate diol contains 0.3% or more and 5.0% or less of a terminal vinyl group based on the total amount of terminal groups.
The urethane (meth) acrylate according to [1] or [2].
[4]
The polycarbonate diol contains 95.0% or more and 99.5% or less of primary terminal hydroxyl groups with respect to the total amount of terminal groups, and has a number average molecular weight of 300 or more and 5000 or less.
The urethane (meth) acrylate according to any one of [1] to [3].
[5]
The isocyanate compound is one or more selected from the group consisting of an aliphatic diisocyanate compound and an alicyclic diisocyanate compound.
The urethane (meth) acrylate according to any one of [1] to [4].
[6]
Containing the urethane (meth) acrylate according to any one of [1] to [5],
Curable composition.

  The urethane (meth) acrylate according to the present invention is excellent in flexibility and exhibits excellent wear resistance when used as a coating application or a molded article application.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible. In the present specification, “(meth) acrylate” means both acrylate and the corresponding methacrylate, and “(meth) acryloyl” means both acryloyl and the corresponding methacryloyl.

式中、Ｒ₁は、炭素数２〜２０である、二価の脂肪族炭化水素又は脂環族炭化水素を示す。さらに、式（１）で表される構造単位は、該構造単位の総量に対して、下記式（２）で表される構造単位を、２０モル％以上９０モル％以下含む。

[Urethane (meth) acrylate]
The urethane (meth) acrylate of this embodiment is an isocyanate compound having two or more isocyanate groups in one molecule (hereinafter referred to as “isocyanate compound (a)”, “organic isocyanate”, “organic isocyanate (a)”, “(a ) ”, Polycarbonate diol (hereinafter also referred to as“ polycarbonate diol (b) ”,“ (b) ”), and hydroxyl group-containing (meth) having one or more (meth) acryloyl groups in one molecule. A reaction product of acrylate (hereinafter also referred to as “hydroxyl group-containing (meth) acrylate (c)” or “(c)”). Further, the polycarbonate diol (b) has a structural unit represented by the following formula (1) and a terminal hydroxyl group.

In the formula, R ₁ represents a divalent aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 20 carbon atoms. Furthermore, the structural unit represented by Formula (1) contains 20 mol% or more and 90 mol% or less of the structural unit represented by the following Formula (2) with respect to the total amount of the structural unit.

In the monomer mixture obtained by subjecting the urethane (meth) acrylate of this embodiment to alkali hydrolysis, the content of the allyl alcohol compound represented by the following formula (3) is the total amount (100%) of the monomer mixture. On the other hand, it is preferably 0.01% or more and 3.0% or less, more preferably 0.02% or more and 2.5% or less, and 0.03% or more and 2.0% or less. More preferably, it is 0.05% or more and 1.5% or less. Here, the “monomer mixture obtained by alkali hydrolysis” means a monomer containing an allyl alcohol compound obtained by hydrolyzing urethane (meth) acrylate.
_{CH 2 = CH-R 2 -OH} (3)
(In the formula, R ₂ represents a divalent aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 20 carbon atoms.)

  Examples of the allyl alcohol compound obtained by subjecting the urethane (meth) acrylate of this embodiment to alkaline hydrolysis include 2-propen-1-ol, 3-buten-1-ol, 4-penten-1-ol, And 5-hexen-1-ol, but is not limited thereto.

  Illustrating a specific method for analyzing the content, ethanol and potassium hydroxide are added to the urethane (meth) acrylate of this embodiment, heated in a heating bath at 100 ° C. for 1 hour, and then the reaction solution is cooled to room temperature. And the method of analyzing the liquid obtained by neutralizing with hydrochloric acid by gas chromatography (GC) can be used. That is, the above “alkali hydrolysis” means that urethane (meth) acrylate is treated in the presence of a basic compound such as potassium hydroxide, and preferably further heat-treated. In GC analysis, not all peaks are necessarily identified, and it may be difficult to calculate the content in a strict sense. Therefore, the content of the allyl alcohol compound referred to in the present embodiment refers to the total peak area of the allyl alcohol compound represented by the above formula (3) in the GC analysis, and the sample from the sum of the peak areas of the detected monomers. A value obtained by multiplying by 100 the value obtained by dividing the sum of all peak areas excluding the peak of the solvent used for dilution and the internal standard substance added as required. More specifically, the content can be determined by the method described in the examples.

  When the content is 0.01% or more, the viscosity of the urethane (meth) acrylate is lowered, and the operability of the obtained curable composition and the appearance of the obtained coating film tend to be superior. Moreover, it exists in the tendency which is excellent with the softness | flexibility of the coating film obtained, and low temperature softness | flexibility.

  On the other hand, when the content is 3.0% or less, the strength, chemical resistance, and wear resistance of the resulting curable composition can be controlled in a more preferable range.

  The said content can be adjusted by adjusting the quantity of the vinyl-group terminal of the polycarbonate diol used at the time of urethane (meth) acrylate synthesis | combination, and adding the said allyl alcohol at the time of this urethane (meth) acrylate synthesis | combination.

<Isocyanate compound (a)>
The isocyanate compound (a) (organic isocyanate) of the present embodiment is not particularly limited as long as it is an isocyanate compound having two or more isocyanate groups in one molecule. For example, 2,4-triresin diisocyanate, 2,6- Triresin diisocyanate and mixtures thereof, diphenylmethane-4,4′-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′biphenylene diisocyanate (TODI), crude TDI, Aromatic diisocyanates such as polymethylene polyphenylene polyisocyanate (PMDI) and crude MDI; Aroaliphatic diisocyanates such as xylylene diisocyanate (XDI) and phenylene diisocyanate; 4-4′-methylenebiscyclohexyl diiso Aneto (hydrogenated MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), include aliphatic diisocyanates such as cyclohexane diisocyanate (hydrogenated XDI).

  Moreover, the isocyanate compound which has 3 or more isocyanate groups in 1 molecule as organic isocyanate is also mentioned. The isocyanate compound having three or more isocyanate groups in one molecule is not particularly limited. For example, in addition to the isocyanurate trimer, biuret trimer, trimethylolpropane adduct compound of the isocyanate compound (a), Examples include triphenylmethane triisocyanate, 1-methylbenzol-2,4,6-triisocyanate, and dimethyltriphenylmethane tetraisocyanate. Furthermore, these isocyanate compounds may be used in the form of modified products such as isocyanurate modification and biuret modification.

  The organic isocyanate of this embodiment is preferably selected from one of the organic isocyanates described above, but may be selected from two or more of these organic isocyanates. Moreover, when selecting and using 2 or more types, you may mix and use them sequentially. In particular, from the viewpoint of weather resistance, the organic isocyanate is preferably one or more selected from the group consisting of an aliphatic diisocyanate compound and an alicyclic diisocyanate compound. HDI, IPDI, dodecane diisocyanate, cyclohexane diisocyanate, More preferred are dicyclohexylmethane diisocyanate and mixtures of these isocyanates.

式中、Ｒ₁は、炭素数２〜２０である、二価の脂肪族炭化水素又は脂環族炭化水素を表す。また、式（１）で表される構造単位は、該構造単位の総量（１００モル％）に対して、下記式（２）で表される構造単位を２０モル％以上９０モル％以下含む。

<Polycarbonate diol (b)>
The polycarbonate diol (b) of this embodiment has a structural unit represented by the following formula (1) and a terminal hydroxyl group.

In the formula, R ₁ represents a divalent aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 20 carbon atoms. Moreover, the structural unit represented by Formula (1) contains 20 mol% or more and 90 mol% or less of the structural unit represented by the following Formula (2) with respect to the total amount (100 mol%) of the structural unit.

  By containing 90 mol% or less of the structural unit represented by the formula (2), the copolymerization effect (the arrangement of the two alkylene groups constituting the randomized arrangement makes the arrangement of the carbonate groups irregular, It is surmised that the flexibility of the resulting curable composition for paints is improved due to the fact that the effect is reduced sufficiently. In addition, since the proportion of the structural unit composed of 1,3-propanediol which is amorphous is sufficiently high by including 20 mol% or more of the structural unit represented by the formula (2), it is obtained for a paint. It is assumed that the flexibility of the curable composition is improved.

  As described above, the cured product obtained from the curable composition containing the urethane (meth) acrylate of the present embodiment has a copolymerization effect on the polycarbonate diol (b) of the present embodiment, and is amorphous. Due to the sufficiently high ratio of the properties, polycarbonate diol composed of 1,4-butanediol having a structure similar to the polycarbonate diol (b), polycarbonate diol using 1,6-hexanediol, and the like, and Furthermore, compared with the hardened | cured material obtained from the conventional curable composition containing the polycarbonate diol using 2-methyl 1, 3- propanediol which has a branched structure, it is excellent in a softness | flexibility.

The polycarbonate diol (b) of this embodiment preferably contains a terminal vinyl group in an amount of 0.3% to 5.0%, more preferably 0.5%, based on the total amount of terminal groups (100% by mass). % To 4.0%. Here, the ratio of the terminal vinyl group to the total amount of the terminal groups is also referred to as the terminal vinyl group ratio. In this embodiment, the terminal vinyl group ratio of the polycarbonate diol (b) is obtained by heating the polycarbonate diol (70 g to 100 g) at a temperature of 160 ° C. to 200 ° C. with stirring under a pressure of 0.4 kPa or less. A fraction corresponding to about 1 to 2% by mass of the polycarbonate diol, ie, about 1 g (0.7 to 2 g) of an initial fraction, was obtained, and about 100 g (95 to 105 g) of ethanol was used as a solvent. It is calculated | required as a value calculated by following formula (4) from the value of the peak area of the chromatogram obtained by subjecting the collect | recovered solution to gas chromatography (GC) analysis. More specifically, it can be determined by the method described in the examples.
Terminal vinyl group ratio (%) = B ÷ A × 100 (4)
A: Sum of peak areas of alcohols containing diol (excluding ethanol) B: Sum of peak areas of compounds having one end with a vinyl group and one end with an OH group Similarly to the method for analyzing the OH ratio, the terminal portion of the polycarbonate diol can be removed as an alcohol and evaporated to be obtained as a fraction.

  When the terminal vinyl group ratio of the polycarbonate diol (b) is 0.3% or more, the amount of urethane bonds at the time of urethane (meth) acrylate synthesis decreases, so the viscosity of the resulting urethane (meth) acrylate must be kept low. The operability of the curable composition and the appearance of the coating film tend to be superior. Further, when used as a curable composition, the terminal vinyl group of the polycarbonate diol (b) acts as an active group that contributes to the curing reaction and impairs physical properties such as strength, chemical resistance, and abrasion resistance of the cured product. There is a tendency for the viscosity to be further reduced. On the other hand, the polycarbonate diol (b) has a terminal vinyl group ratio of 5.0% or less, thereby preventing an excessive decrease in the urethane bond amount of the urethane (meth) acrylate, and the strength of the resulting curable composition, It tends to be possible to control the chemical resistance and wear resistance within a more suitable range.

  The method for controlling the terminal vinyl group ratio of the polycarbonate diol (b) to the above-mentioned range is not particularly limited. For example, during or after the polymerization of the polycarbonate diol (b), a predetermined amount of one terminal is a vinyl group. And a method in which a compound having an OH group at one end is added and heat-treated. The compound in which one end is a vinyl group and one end is an OH group is not particularly limited, and examples thereof include 2-propen-1-ol, 3-buten-1-ol, 4-penten-1-ol, and 5-hexen-1-ol is mentioned. Further, by depressurizing at high temperature during the synthesis of the polycarbonate diol (b), a dehydration reaction of the terminal primary alcohol can be caused to generate a terminal vinyl group.

The polycarbonate diol (b) of the present embodiment preferably contains 94.0% or more and 99.5% or less of the primary terminal hydroxyl group (hydroxyl group, OH group) with respect to the total amount of terminal groups (100%). More preferably, it is 94.0% or more and 98.0% or less, and more preferably 95.0% or more and 97.0% or less. Here, the ratio of the primary terminal hydroxyl group to the total amount of the terminal groups is also referred to as the primary terminal OH ratio. In this embodiment, the primary terminal OH ratio of the polycarbonate diol (b) is obtained by heating the polycarbonate diol (70 g to 100 g) at a temperature of 160 ° C. to 200 ° C. with stirring under a pressure of 0.4 kPa or less. A fraction corresponding to about 1 to 2% by mass of the polycarbonate diol, that is, about 1 g (0.7 to 2 g) of an initial fraction was obtained, and about 100 g (95 to 105 g) of ethanol was used as a solvent. It collect | recovers using, and it calculates | requires as a value computed by following formula (5) from the value of the peak area of the chromatogram obtained by subjecting the collect | recovered solution to a gas chromatography (GC) analysis. More specifically, it can be determined by the method described in the examples.
Primary terminal OH ratio (%) = C ÷ A × 100 (5)
A: Sum of peak areas of diol-containing alcohols (excluding ethanol) C: Sum of peak areas of diols with both ends being primary OH groups Primary terminal OH ratio is the total amount of terminal hydroxyl groups in polycarbonate diol As shown above, when the polycarbonate diol is heated to a temperature of 160 ° C. to 200 ° C. under a pressure of 0.4 kPa or less, the terminal portion of the polycarbonate diol comes off as an alcohol. And can be obtained as a fraction.

  When the primary terminal OH ratio of the polycarbonate diol (b) is 94.0% or more, the curing rate of the curable composition is improved and the productivity tends to be increased. Moreover, it exists in the tendency for the surface hardness of the obtained hardened | cured material, abrasion resistance, and chemical resistance to be more excellent. When the primary terminal OH ratio of the polycarbonate diol (b) is 99.5% or less, the viscosity of the resulting curable composition can be kept low, and the operability of the curable composition tends to be superior. . In addition, the curing reaction progresses uniformly, suppresses the occurrence of gels and blisters, the appearance of the cured product becomes better, and the cured product becomes more uniform. It tends to be excellent.

  The method for controlling the primary terminal OH ratio of the polycarbonate diol (b) to the above-mentioned range is not particularly limited. For example, a predetermined amount of monoalcohol is added during or after the polymerization of the polycarbonate diol (b). Examples thereof include a method of heat treatment and a method of adding a small amount of a secondary diol to the polymerization diol of the polycarbonate diol (b).

  As the polycarbonate diol (b) of this embodiment, 1,3-propanediol is used as a main raw material by various methods described in, for example, Schell, Polymer Review Vol. 9, pages 9 to 20 (1964). As a polycarbonate diol.

（式中、Ｒ₁は、炭素数２又は４〜２０である、二価の脂肪族又は脂環族炭化水素を示す。） The polycarbonate diol (b) of this embodiment can be synthesized by a transesterification reaction with a carbonate compound using 1,3-propanediol and a diol containing a diol represented by the following formula (6) as raw materials. .

(In the formula, R ₁ represents a divalent aliphatic or alicyclic hydrocarbon having 2 or 4 to 20 carbon atoms.)

  Specific examples of the diol represented by the above formula (6) used in the present embodiment are not particularly limited. For example, ethylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1 , 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,8-octane Diol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2-ethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentane Diol, 2,4-diethyl-1,5-pentanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1, - cyclohexanedimethanol, and 2-bis (4-hydroxycyclohexyl) - propane. The diol represented by the formula (6) may be used alone or in combination of two or more. Among these, it is preferable to use a linear alkylene diol having 2 or 4 to 10 carbon atoms. Among these, it is more preferable to use 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

  As a carbonate compound used for the synthesis | combination of the carbonate diol (b) of this embodiment, a phosgene, chloroformate, an aliphatic carbonate compound, and an aromatic carbonate compound can be used, for example. From the viewpoint of safety and the like, preferably, aliphatic carbonate compounds and aromatic carbonate compounds such as dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, and trimethylene carbonate are used. In order to adjust the primary terminal OH ratio of the polycarbonate diol (b) to 94.0% or more and 99.5% or less, more preferably dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and diphenyl carbonate are used. When a dialkyl carbonate is used as the carbonate compound used in the production of the carbonate diol of this embodiment, the alkyl group residue derived from the dialkyl carbonate remains at the end of the polycarbonate diol (b), so that the primary terminal OH ratio is Is adjusted to 94.0% or more and 99.5% or less. Even when cyclic carbonate compounds such as ethylene carbonate, propylene carbonate, and trimethylene carbonate are used, residues derived from these carbonate compounds remain at the ends of the polycarbonate diol, but the terminal groups in this case become primary hydroxyl groups. Therefore, it is preferable to adjust the primary terminal OH ratio to 99.5% or less by adjusting the amount and type of impurities of the diol used.

  In the above-described transesterification reaction, it is desirable to use a catalyst when it is desired to speed up the reaction. The catalyst is not particularly limited. For example, titanium compounds such as tetraisopropoxy titanium and tetra-n-butoxy titanium; tin compounds such as di-n-butyltin dilaurate, di-n-butyltin oxide and dibutyltin diacetate; acetic acid Examples thereof include metal salts of acetic acid such as magnesium, calcium acetate, and zinc acetate. Among these, it is preferable to use a titanium compound. These catalysts are preferably used in an amount of 1.0 mass ppm to 300 mass ppm, more preferably 30 mass ppm to 200 mass ppm, based on the total amount of the polycarbonate diol raw material.

  The number average molecular weight of the polycarbonate diol (b) of the present embodiment is preferably 300 or more and 5000 or less, more preferably 500 or more and 4000 or less, and still more preferably 1000 or more and 3000 or less. When the number average molecular weight of the polycarbonate diol (b) is 300 or more, the flexibility of the coating film becomes better and the soft feeling tends to be more excellent. Further, when the number average molecular weight of the polycarbonate diol (b) is 5000 or less, the reaction at the time of curing can be accelerated, the curing time can be shortened, and the viscosity of the curable composition can be lowered. It tends to be excellent.

  The method for controlling the number average molecular weight of the polycarbonate diol (b) within the above range is not particularly limited, and examples thereof include a method for controlling the amount of diol monomer distilled off during polymerization of the polycarbonate diol (b). The number average molecular weight of the polycarbonate diol (b) is measured by the method described in Examples described later.

  The polycarbonate diol (b) of this embodiment contains 95.0% or more and 99.5% or less of primary terminal hydroxyl groups with respect to the total amount (100%) of end groups, and the number average molecular weight is 300. When it is 5,000 or less, the viscosity of the curable composition and the flexibility of the cured product, and the strength and abrasion resistance of the cured product tend to be compatible.

  In this embodiment, as a raw material for the polycarbonate diol (b), in addition to the diol, a compound having three or more hydroxyl groups per molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, glycerin. A polycarbonate polyol that is polyfunctionalized so that the average number of hydroxyl groups in one molecule is 2 or more is also included by using a small amount of.

<Hydroxyl group-containing (meth) acrylate (c)>
The hydroxyl group-containing (meth) acrylate (c) of the present embodiment is not particularly limited as long as it has one or more hydroxyl groups and one or more (meth) acryloyl groups in one molecule. -Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, hydroxyhexyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxy Propyl acrylate, 1,4-butylene glycol monoacrylate, glycerin monoacrylate, propylene glycol monoacrylate, polycaprolactone glycol monoacrylate, trimethylolpropane diacrylate Pentaerythritol triacrylate, ditrimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and methacrylates corresponding to these acrylates like. Moreover, even if it is another thing, if it is a (meth) acrylate monomer containing a hydroxyl group, it can be used as a hydroxyl-containing (meth) acrylate.

  In addition, the hydroxyl group-containing (meth) acrylate (c) of the present embodiment is not particularly limited, but those having two or more (meth) acryloyl groups in one molecule can also be used. Specific examples of the hydroxyl group-containing (meth) acrylate (c) having two or more (meth) acryloyl groups in one molecule are not particularly limited. For example, trimethylolpropane diacrylate, 2-hydroxy-3-acryloyloxy Examples thereof include propyl acrylate, pentaerythritol triacrylate, ditrimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and methacrylates corresponding to these acrylates and glycerin diacrylate. In addition, other (meth) acrylate monomers containing a hydroxyl group and having two or more (meth) acryloyl groups in one molecule may also be used as the hydroxyl group-containing (meth) acrylate (c). it can. These can also be used individually by 1 type and can also use 2 or more types together.

  The hydroxyl group-containing (meth) acrylate (c) is a compound of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and urethane (meth) acrylate to be obtained and a curable composition containing the same. More preferred are hydroxypropyl acrylate, 3-hydroxybutyl acrylate, pentaerythritol triacrylate, and 4-hydroxybutyl acrylate, and methacrylates corresponding to these acrylates.

[Method for producing urethane (meth) acrylate]
The urethane (meth) acrylate production method of the present embodiment includes an isocyanate compound (a) having two or more isocyanate groups in one molecule, a polycarbonate diol (b), and one or more (meth) acryloyl groups in one molecule. And a hydroxyl group-containing (meth) acrylate (c) having a reaction step to obtain a reaction product. A reaction process is not specifically limited, It can carry out by a well-known method. As the reaction step, for example, a step of reacting an isocyanate compound (a) with a polycarbonate diol (b) to obtain a prepolymer having a terminal isocyanate group, and then a hydroxyl group-containing (meth) acrylate is added to the prepolymer. The method of performing by dividing into the process of making (c) react is mentioned.

  In the reaction step of the present embodiment, the blending amount of the isocyanate compound (a) is based on the ratio of isocyanate groups (isocyanate groups / hydroxyl groups) of the isocyanate compound (a) to the total hydroxyl groups of the polycarbonate diol (b). It is preferable to determine. Here, (isocyanate group / hydroxyl group) is preferably 1.5 or more and 5.0 or less, more preferably 1.8 or more and 3.0 or less, and further preferably 1.9 or more and 2.1 or less. It is as follows. When the (isocyanate group / hydroxyl group) is 1.5 or more, the increase in the molecular weight is excessive and the increase in viscosity is suppressed, and the viscosity of the resulting curable composition is increased and the operability is increased. Tend to be able to suppress inferiority. Further, the curing time of the resulting curable composition does not become too long, and the resulting cured product tends to be excellent in mechanical strength, wear resistance, and chemical resistance. On the other hand, when (isocyanate group / hydroxyl group) is 5.0 or less, the unreacted isocyanate compound (a) is suppressed, and the resulting curable composition becomes too hard and the flexibility is impaired. It tends to be suppressed. Moreover, in the range which does not impair the effect of this invention, polyester polyol and polyether polyol can also be used simultaneously with polycarbonate diol (b).

  In this embodiment, it is preferable that the compounding quantity of the hydroxyl-containing (meth) acrylate (c) in the reaction process is determined using the hydroxyl equivalent as an index. When comparing with the isocyanate group equivalent of the prepolymer (terminal isocyanate group polymer) obtained by the reaction of the isocyanate compound (a) and the polycarbonate diol (b), the hydroxyl group-containing (meth) acrylate of the isocyanate group It is preferable to determine the ratio of hydroxyl groups (hydroxyl group / isocyanate group) as an index. Here, (hydroxyl group / isocyanate group) is preferably 0.8 or more and 1.5 or less, and more preferably 1.0 or more and 1.3 or less. When the (hydroxyl group / isocyanate group) is 1.5 or less, the hydroxyl group-containing (meth) acrylate (c) is easily incorporated into the structure of the urethane (meth) acrylate, and those existing as an acrylic monomer are reduced. There is a tendency to ensure the freedom of formulation design. However, when a hydroxyl group-containing (meth) acrylate (c) that is not incorporated into the structure of urethane (meth) acrylate is intentionally used as a blending constituent material of the coating composition or molding composition, (hydroxyl group / isocyanate group) ) May exceed 1.5. Moreover, when (hydroxyl group / isocyanate group) is 0.8 or more, there is a tendency that a large number of isocyanate groups remain at the terminal of the polymer.

  Reaction between isocyanate group (a) and / or prepolymer, which is a reaction product of isocyanate compound (a) and polycarbonate diol, with hydroxyl group of hydroxyl group-containing (meth) acrylate (c), so-called urethane The temperature during the reaction is preferably 120 ° C. or lower. When this temperature is 120 ° C. or lower, the reaction rate control tends to be easy, the high molecular weight proceeds more than necessary, the reaction product is thickened, a gel is formed, And it tends to be able to suppress the cause of coloring due to alteration. The temperature is more preferably 40 ° C. or higher and 110 ° C. or lower, and further preferably 40 ° C. or higher and 80 ° C. or lower. Furthermore, when the temperature is 40 ° C. or higher, the reaction rate becomes extremely slow, the viscosity of the reactant becomes too high, dispersion and mixing become insufficient, and a uniform product cannot be obtained. It tends to be suppressed.

  In the urethane reaction, a urethane reaction catalyst can be added and used as necessary. The urethane reaction catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine; metal salts such as potassium acetate, zinc stearate and tin octylate; and organometallic compounds such as dibutyltin dilaurate and dioctyltin dilaurate. When using a urethane reaction catalyst, the addition amount thereof is preferably 0.5 mass ppm or more and 2000 mass ppm or less with respect to the reaction product.

  Moreover, an organic solvent can be used in the case of a urethane reaction as needed. Examples of the organic solvent include, but are not limited to, ester systems such as butyl acetate and ethyl acetate; ketone systems such as methyl ethyl ketone and acetone; and aromatic organic solvents such as toluene and xylene. These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When using an organic solvent, it is desirable not to use it more than necessary in order to cope with the environment by reducing VOC. A preferable usage amount is 5.0% by mass or more and 150% by mass or less with respect to the entire raw material (100% by mass) of urethane (meth) acrylate. Furthermore, a radical polymerization inhibitor can also be used. The radical polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone monomethyl ether and phenothiazine. These radical polymerization inhibitors are preferably added to such an extent that they do not affect the curing reaction, and are specifically 1000 ppm by mass or less with respect to the entire raw material of urethane (meth) acrylate.

[Composition composition]
The urethane (meth) acrylate of the present embodiment can be used alone, but in order to adjust the viscosity according to the use, and for the purpose of adjusting physical properties such as the crosslinking density of the obtained resin, the urethane (meth) acrylate of the present embodiment ( An appropriate (meth) acrylic acid ester (hereinafter referred to as “other (meth) acrylate”) other than the urethane (meth) acrylate of the present embodiment may be blended with the (meth) acrylate to prepare a blended composition. it can. Other (meth) acrylates are not particularly limited. For example, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and 1,9-diacrylate. Diacrylate esters such as nonanediol, neopentyl glycol diacrylate, methylpentanediol diacrylate, tetraethylene glycol diacrylate, cyclohexanedimethanol diacrylate, polyethoxylate bisphenol A diacrylate, polyproxy hydrogenated bisphenol A diacrylate, and the like Dimethacrylic acid ester corresponding to: trimethylolpropane triacrylic acid ester, pentaerythritol triacrylic acid ester, pentaerythritol ester Polyfunctional acrylates such as acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like, and corresponding polyfunctional methacrylate; tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, acrylic Acrylic acid esters such as cyclohexyl acid, isobornyl acrylate, benzyl acrylate, phenyl acrylate, and the corresponding methacrylic acid ester vinyl acetate; vinyl ester monomers such as vinyl butyrate and divinyl adipate; acrylamide, N-vinylformaldehyde Acrylamide such as N-vinyl-2-pyrrolidone and Nt-butylacrylamide. Although the compounding quantity of (meth) acrylate is not specifically limited unless the effect of the urethane (meth) acrylate of this embodiment is impaired, it is the total amount (100 mass%) with the urethane (meth) acrylate of this embodiment. On the other hand, it is preferable that it is 5.0 mass% or more and 90 mass% or less, More preferably, it is 10 mass% or more and 80 mass% or less. When the blending amount is 5.0% by mass or more, the effect of dilution tends to be obtained, and when the blending amount is 90% by mass or less, the effect of the urethane (meth) acrylate of this embodiment is ensured. There is a tendency to play. When mix | blending other (meth) acrylate, you may mix | blend in the reaction process for obtaining the urethane (meth) acrylate of this embodiment, and you may mix | blend when setting it as a subsequent compounding composition.

(Curable composition)
The curable composition of this embodiment contains the urethane (meth) acrylate of this embodiment. Since the urethane (meth) acrylate of this embodiment has a double bond of a (meth) acryloyl group, for example, the urethane (meth) acrylate of this embodiment alone or a blended composition contains, for example, a thermal polymerization initiator and is heated. By doing, it can be hardened and a hardened material can be obtained. It is also possible to obtain a cured product by easily curing in a short time by containing a photopolymerization initiator instead of a thermal polymerization initiator and irradiating it with ultraviolet rays using an ultraviolet fluorescent lamp or a high pressure mercury lamp. . The concentration of the polymerization initiator of these thermal polymerization initiators or photopolymerization initiators is preferably 0.1% by mass or more and 20% by mass or less with respect to the total amount (100% by mass) of urethane (meth) acrylate, More preferably, it is 1.0 mass% or more and 10 mass% or less, More preferably, it is 3.0 mass% or more and 5.0 mass% or less. When the concentration of the polymerization initiator is 0.1% by mass or more, it tends to be cured, and when the concentration of the polymerization initiator is 20% by mass or less, each characteristic of the obtained cured product. Tend to be good.

  The thermal polymerization initiator is not particularly limited. For example, peroxides such as benzoyl peroxide, lauroyl peroxide, bis- (4-t-butylcyclohexyl) peroxydicarbonate, and 2,2′-azobis- Examples thereof include azo compounds such as isobutyronitrile and 2,2′-azobis-2,4-dimethylvaleronitrile. These thermal polymerization initiators can be used alone or in combination of two or more. Although the heating temperature at the time of thermal polymerization varies depending on the adhesion or the substrate to be applied, it is preferably from room temperature to 90 ° C, more preferably from 40 to 80 ° C.

  The photopolymerization initiator is not particularly limited. For example, benzophenone, ω-bromoacetophenone, chloroacetone, acetophenone, diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethyl Aminopropiophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl Ether, benzoin-n-butyl ether, benzyl methyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- Emissions, methylbenzoyl formate, 2,2-diethoxyacetophenone, 4-N, carbonyl-based photopolymerization initiators such as N'- dimethyl acetophenone. Furthermore, sulfide photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide and tetraethylmethylammonium sulfide; quinone photopolymerization initiators such as benzoquinone, t-butylanthraquinone and 2-ethylanthraquinone; 2,2′-azobispropane Azo photopolymerization initiators such as hydrazine; thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone; peroxide photopolymerization initiators such as benzoyl peroxide and di-t-butyl peroxide Agents. These photoinitiators can be used individually by 1 type or in combination of 2 or more types.

  Furthermore, if necessary, a photopolymerization initiator and a known photosensitizer can be used in combination. The photosensitizer is not particularly limited, and examples thereof include 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone, and a curable composition. When obtaining a product, the amount of addition can be determined within a range that does not impair the effects of the present invention.

  Moreover, the urethane (meth) acrylate of this embodiment may be cured without using a polymerization initiator. For example, a cured product can be obtained by irradiation with an electron beam.

  The curable composition of this embodiment can further contain, for example, an antioxidant or a light stabilizer such as hindered amines, hindered phenols, and benzotriazoles for the purpose of improving storage stability. Examples of these include, but are not limited to, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, and ADK STAB AO. -330, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 329A, ADK STAB 1500, ADK STAB C, ADK STAB 135A, 3010 (above, trade name manufactured by Asahi Denka Kogyo Co., Ltd.) Sumilyzer BHT, Sumilyzer S, Sumilyzer BP-76, Sumilyzer MDP-S, Smizer GM, Summarizer BBM-S, Summarizer WX-R, Summarizer NW, Summarizer BP-101, Summarizer GA-80, Summarizer TNP, Summarizer BP-179, Summarizer TPP-R, Summarizer P-16 (above, manufactured by Sumitomo Chemical Co., Ltd.) Product name) Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622, Tinuvin 111, Tinuvin 123, Tinuvin 292 (above, product names manufactured by BASF Japan Ltd.) are listed. The content of these antioxidants and light stabilizers is not particularly limited, but is preferably 0.001% by mass to 5.0% by mass with respect to the total amount (100% by mass) of the curable composition. .

  In the curable composition of the present embodiment, for example, fillers, flame retardants, dyes, pigments of organic and inorganic pigments, mold release agents, fluidity modifiers, plasticizers, antifoaming agents, Leveling agents, colorants, and inert organic solvents can be included.

  The filler or pigment is not particularly limited, but for example, woven fabric, glass fiber, carbon fiber, polyamide fiber, mica, kaolin, bentonite, metal powder, azo pigment, carbon black, clay, silica, talc, gypsum, alumina Examples thereof include white and barium carbonate, and other commonly used fillers and pigments.

  Although it does not specifically limit as a mold release agent, a fluidity | liquidity adjusting agent, and a leveling agent, For example, polysiloxane like silicone, aerosil, a wax, a stearate, BYK-331 (BYK Chemical company make) is mentioned. It is done.

  Specific examples of the plasticizer are not particularly limited. For example, phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, and diisononyl phthalate. : Phosphate esters such as tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, tris-chloroethyl phosphate, tris-dichloropropyl phosphate: trimellitic acid octyl ester, trimellitic acid Isodecyl ester, trimellitic acid ester, dipentaerythritol ester, dioctyl adipate, dimethyl azide Fatty acid esters such as pete, di-2-ethylhexyl azelate, dioctyl azelate, dioctyl sebacate, di-2-ethylhexyl sebacate, and methyl acetyl ricinoate: pyromellitic esters such as pyromellitic octyl ester: epoxy Epoxy plasticizers such as hydrogenated soybean oil, epoxidized linseed oil, and epoxidized fatty acid alkyl esters: polyether plasticizers such as adipic acid ether esters and polyethers Plasticizers: liquid rubbers such as liquid NBR, liquid acrylic rubber, and liquid polybutadiene : Non-aromatic paraffin oil can be mentioned.

  In order to adjust the workability at the time of coating, the curable composition of this embodiment can further contain an inert organic solvent as necessary. The content of the inert organic solvent is preferably 1.0% by mass or more and 90% by mass or less, more preferably 15% by mass or more and 75% by mass or less, with respect to the total amount (100% by mass) of the curable composition. More preferably, it is 30 mass% or more and 60 mass% or less. Although it does not specifically limit as an inert organic solvent, For example, it is preferable that it is an organic solvent which is substantially inert with respect to a polyisocyanate compound, and does not have active hydrogen. Specific examples thereof include, but are not limited to, hydrocarbons such as pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, cyclohexane, and methylcyclohexane; trichlorofluoroethane, tetrachloro Fluorinated inert liquids such as fluorinated oils such as difluoroethane and perfluoroether; perfluorocyclohexane, perfluorobutyltetrahydrofuran, perfluorodecalin, perfluoro-n-butylamine, perfluoropolyether, and dimethylpolysiloxane. Also included are methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, and xylene. These inert organic solvents can be used individually by 1 type or in combination of 2 or more types.

  For example, when the curable composition of this embodiment is used for a coating application, it can be applied to a target object to be coated using a commonly used technique such as spraying or a coater. Moreover, when using for a shaping | molding use, it can obtain as a molding material by pouring the curable composition of this embodiment mainly into a formwork.

  Hereinafter, the present embodiment will be described in more detail based on examples, but the present embodiment is not limited to the following examples. First, the physical properties and measurement methods for evaluation and evaluation criteria will be described below.

(Physical property 1) Number average molecular weight of polycarbonate diol Using polycarbonate diol as a sample, the hydroxyl value (OH value) was determined according to JIS K1557-1, and the number average molecular weight was calculated using the following formula (7).
Number average molecular weight = 2 / (OH value × 10 ⁻³ /56.1) (7)

(Physical property 2) Ratio of terminal vinyl group of polycarbonate diol and ratio of primary terminal hydroxyl group The ratio of terminal vinyl group in polycarbonate diol and the ratio of primary terminal hydroxyl group (primary terminal OH ratio) were determined as follows. . First, 70 g to 100 g of polycarbonate diol was measured in a 300 mL eggplant flask. Using a rotary evaporator to which a trap ball for collecting fractions is connected, the polycarbonate diol in the eggplant flask is heated in a heating bath at about 180 ° C. under a pressure of 0.4 kPa or less and stirred to form a trap ball. A fraction corresponding to about 1 to 2% by mass of the polycarbonate diol, that is, about 1 g (0.7 to 2 g) of an initial fraction was obtained. The obtained fraction was dissolved in about 100 g (95 to 105 g) of ethanol and recovered as a solution. The collected solution was subjected to gas chromatography analysis (hereinafter also referred to as “GC analysis”), and the peak area value of the obtained chromatograph was used to calculate the terminal vinyl group ratio in the polycarbonate diol according to the following formula (4). The primary terminal OH group ratio in the polycarbonate diol was calculated from the following formula (5). GC analysis uses DB-WAX (trade name, manufactured by J & W, USA) 30 m as a column, gas chromatography 6890 (trade name, manufactured by Hewlett-Packard, USA) with a film thickness of 0.25 μm, and a hydrogen flame as a detector. An ionization detector (FID) was used. The temperature rising profile of the column was a profile that was raised from 60 ° C. to 250 ° C. at 10 ° C./min and then held at that temperature for 15 minutes. Identification of each peak in the GC analysis was performed using the following GC-MS apparatus. The GC device used 6890 (trade name, manufactured by Hewlett-Packard, USA) with DB-WAX (trade name, manufactured by J & W, USA) as a column. In the GC apparatus, the temperature was raised from an initial temperature of 40 ° C. to 220 ° C. at a heating rate of 10 ° C./min. As the MS apparatus, Auto-massSUN (trade name, manufactured by JEOL, Japan) was used. In the MS apparatus, the measurement was performed with an ionization voltage of 70 eV, a scan range of m / z = 10 to 500, and a photomultiplier gain of 450V.
Terminal vinyl group ratio (%) = B ÷ A × 100 (4)
A: Sum of peak areas of alcohols including diol (excluding ethanol) B: Sum of peak areas of compounds having one end with a vinyl group and one end with an OH group Primary terminal OH ratio (%) = C ÷ A × 100 (5)
C: Sum of peak areas of diols in which both ends are primary OH groups

(Physical property 3) Content of allyl alcohol compound in the total monomer mixture obtained by alkali hydrolysis of urethane (meth) acrylate About 1.0 g of urethane (meth) acrylate was measured in a 100 cc eggplant flask, and 30 g of ethanol was measured. 3.95 g of potassium hydroxide was added and heated in a heating bath at about 100 ° C. for 1 hour with stirring. The reaction solution was cooled to room temperature, neutralized with hydrochloric acid, cooled in a refrigerator for 1 hour, and precipitated potassium chloride was filtered. The obtained filtrate was subjected to GC analysis under the same conditions as the analysis of the vinyl group terminal ratio and primary OH terminal ratio of the polycarbonate diol. 100 times the value obtained by dividing the total peak area of the allyl alcohol compound by the sum of the peak areas of the detected monomers (the sum of the total peak areas minus the peak area of the solvent used to dilute the sample) The content (%) of the allyl alcohol compound was determined.

(Evaluation 1) Tensile breaking strength and breaking elongation Each photopolymerization curable composition prepared in each Example and Comparative Example was used as a sample. Using an applicator, the curable composition was applied onto a glass plate so that the film thickness was 40 μm after curing, and UV was applied at an energy of 1000 mJ / W using a UV irradiation machine (Oak Manufacturing Co., Ltd., Handy UV-300). A film of cured product was obtained by photopolymerization and peeling. After leaving at room temperature for 24 hours, a sample having a width of 6.6 mm and a length of 60 mm was cut out from this film to obtain a sample film. Using a Universal Testing Machine (manufactured by Zwick Corp.) in a constant temperature room at 23 ° C., the tensile breaking strength (MPa) and elongation at break (%) of the sample film at a chucking speed of 20 mm and a tensile speed of 5 mm / min. And measured. This sample film was also used for evaluating (low temperature) flexibility and oil resistance.

(Evaluation 2) Flexibility Tests were conducted by the method shown in (Evaluation 1) above, and the stress (MPa) at 50% elongation (25 mm elongation) was measured. The lower the stress, the higher the flexibility.

(Evaluation 3) Low-temperature flexibility A low-temperature thermostatic oven was attached to the measurement site of the tensile rupture strength measuring apparatus of (Evaluation 1) above, and the measurement was performed at -20 ° C. The stress (MPa) at 50% elongation (25 mm elongation) was measured. The lower the stress, the better the low temperature flexibility.

(Evaluation 4) Oil resistance The oil resistance (swelling rate) after immersing the sample film of the above (Evaluation 1) in oleic acid at 23 ° C. for 1 week was measured. The oil resistance (swell ratio) was determined using the following formula (8).
Oil resistance (%) = {(mass after test−mass before test) / mass before test} × 100 (8)

(Evaluation 5) Film surface hardness The photopolymerization curable composition of the above (Evaluation 1) was applied onto a polycarbonate plate having a thickness of about 2 mm so that the film thickness after curing with an applicator was about 30 μm. UV photopolymerization was performed with an energy of 1000 mJ / W using an Oak Manufacturing Co., Ltd., Handy UV-300) to obtain a cured coating film. After the cured coating film was dried at room temperature for 24 hours, the pencil hardness was measured and evaluated in accordance with JIS K-5400.

(Evaluation 6) Appearance of cured coating film The surface of the cured coating film prepared by the same operation as in the above (Evaluation 5) was visually observed. X (defect) where fine irregularities such as orange peel were noticeable, △ (somewhat good) where slight irregularities such as orange peel were seen, and fine irregularities such as orange peel were recognized What was not evaluated was evaluated as ○ (good).

(Evaluation 7) Abrasion resistance A cured coating film obtained by the same operation as in the above (Evaluation 5) was evaluated according to the JIS K5600 wear wheel method (wear wheel CS-10, weight 500 g, 500 rotations). The reduction mass measurement result (mg) in the test was used as the evaluation result of wear resistance.

(Evaluation 8) Soft feeling The soft feeling was evaluated by the touch when the surface of the cured coating film obtained by the same operation as in the above (Evaluation 5) was touched by hand. The determination result was expressed as follows.
○: A good soft feeling is felt.
Δ: A relatively good soft feeling is felt.
X: Not felt soft.

[Polymerization Example 1] PC1
In a 2 L glass flask equipped with a rectification column packed with an ordered packing and a stirrer, 456.5 g (6 mol) of 1,3-propanediol (1,3-PDO), 1,4-butanediol (1 , 4-BDO) 360.5 g (4 mol) and ethylene carbonate 1030 g (11.7 mol) were charged and dissolved by stirring at 70 ° C., and then 0.10 g of titanium tetrabutoxide was added as a catalyst. The mixture was heated in an oil bath set at 175 ° C., and the reaction was carried out for 12 hours while part of the fraction was removed from the reflux head at a reflux ratio of 4 at an internal temperature of the flask of 140 ° C. and a degree of vacuum of 1.0 to 1.5 kPa. Thereafter, the rectification column was replaced with a simple distillation apparatus, heated in an oil bath set at 180 ° C., the flask was cooled to an internal temperature of 140 to 150 ° C., and the vacuum level was reduced to 0.5 kPa. Carbonate was removed. Thereafter, the setting of the oil bath was raised to 220 ° C., and the reaction was further performed for 2 hours while removing the diol produced at an internal temperature of the flask of 210 ° C. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC1.

[Polymerization Example 2] PC2
In a 2 L glass flask equipped with a rectification column packed with an ordered packing and a stirrer, 456.5 g (6 mol) of 1,3-propanediol (1,3-PDO), 1,4-butanediol (1 , 4-BDO) 360.5 g (4 mol) and 1053.9 g (11.7 mol) of dimethyl carbonate were stirred and dissolved at 70 ° C., and then 0.10 g of titanium tetrabutoxide was added as a catalyst. Then, it heated and stirred at the temperature of 140-150 degreeC under normal pressure, and was made to react for 7 hours, distilling off the mixture of methanol and dimethyl carbonate to produce | generate. Thereafter, the reaction temperature was 150 ° C. to 190 ° C., the pressure was 10 to 15 kPa, and the reaction was performed for 3 hours while distilling off the mixture of methanol and dimethyl carbonate to be produced. Then, it was made to react at 210 degreeC for 2 hours, reducing pressure gradually to 0.5kPa. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC2.

[Polymerization Example 3] PC3
The reaction was carried out by the method shown in Polymerization Example 2 for polycarbonate diol, except that 416.6 g (4 mol) of 1,5-pentanediol (1,5-PDO) was used instead of 1,4-butanediol. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC3.

[Polymerization Example 4] PC4
The reaction was carried out by the method shown in Polymerization Example 2 of polycarbonate diol, except that 47,7 g (4 mol) of 1,6-hexanediol (1,6-HDO) was used instead of 1,4-butanediol. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC4.

[Polymerization Example 5] PC5
Polycarbonate except that the amount of 1,3-propanediol (1,3-PDO) was 608.7 g (8 mol) and the amount of 1,4-butanediol (1,4-BDO) was 180.2 g (2 mol) The reaction was carried out by the method shown in polymerization example 2 of diol. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC5.

[Polymerization Example 6] PC6
Polycarbonate except that the amount of 1,3-propanediol (1,3-PDO) was 228.2 g (3 mol) and the amount of 1,4-butanediol (1,4-BDO) was 630.8 g (7 mol) The reaction was carried out by the method shown in polymerization example 2 of diol. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC6.

[Polymerization Example 7] PC7
In a 2 L glass flask equipped with a rectification column packed with a regular packing and a stirrer, 456.5 g (6 mol) of 1,3-propanediol (1,3-PDO), 1,4-butanediol (1, 4-BDO) 360.5 g (4 mol) and dimethyl carbonate 1053.9 g (11.7 mol) were charged and dissolved by stirring at 70 ° C., and then 0.10 g of titanium tetrabutoxide was added as a catalyst. Then, it heated and stirred at the temperature of 140-150 degreeC under normal pressure, and was made to react for 7 hours, distilling off the mixture of methanol and dimethyl carbonate to produce | generate. Thereafter, the reaction temperature was 150 ° C. to 190 ° C., the pressure was 10 to 15 kPa, and the reaction was performed for 3 hours while distilling off the mixture of methanol and dimethyl carbonate produced. Furthermore, it was made to react at 210 degreeC for 1 hour, and 1, 3- propanediol was distilled off. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC7.

[Polymerization Example 8] PC8
In a 2 L glass flask equipped with a rectification column packed with an ordered packing and a stirrer, 456.5 g (6 mol) of 1,3-propanediol (1,3-PDO), 1,4-butanediol (1 , 4-BDO) 360.5 g (4 mol) and ethylene carbonate 1030 g (11.7 mol) were charged and dissolved by stirring at 70 ° C., and then 0.10 g of titanium tetrabutoxide was added as a catalyst. The mixture was heated in an oil bath set at 175 ° C., and the reaction was carried out for 12 hours while part of the fraction was removed from the reflux head at a reflux ratio of 4 at an internal temperature of the flask of 140 ° C. and a degree of vacuum of 1.0 to 1.5 kPa. Thereafter, the rectification column was replaced with a simple distillation apparatus, heated in an oil bath set at 180 ° C., the flask was cooled to an internal temperature of 140 to 150 ° C., and the vacuum level was reduced to 0.5 kPa. The carbonate was removed. Then, the setting of the oil bath was raised to 180 ° C., and the reaction was further performed for 4 hours while removing the produced diol at an internal temperature of the flask of 175 ° C. After setting to normal pressure, 5.8 g (0.05 mol) of 1-heptanol was added, and the reaction was performed at an internal temperature of the flask of 165 ° C. for 3 hours. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC8.

[Polymerization Example 9] PC9
In a 2 L glass flask equipped with a rectification column packed with an ordered packing and a stirrer, 456.5 g (6 mol) of 1,3-propanediol (1,3-PDO), 1,4-butanediol (1 , 4-BDO) 360.5 g (4 mol) and 1053.9 g (11.7 mol) of dimethyl carbonate were stirred and dissolved at 70 ° C., and then 0.10 g of titanium tetrabutoxide was added as a catalyst. Then, it heated and stirred at the temperature of 140-150 degreeC under normal pressure, and was made to react for 7 hours, distilling off the mixture of methanol and dimethyl carbonate to produce | generate. Thereafter, the reaction temperature was 150 ° C. to 190 ° C., the pressure was 10 to 15 kPa, and the reaction was performed for 3 hours while distilling off the mixture of methanol and dimethyl carbonate to be produced. Then, it was made to react at 210 degreeC for 2 hours, reducing pressure gradually to 0.5kPa. After the atmospheric pressure was reached, 3.88 g (0.045 mol) of 4-penten-1-ol was added, and the reaction was performed at a flask internal temperature of 165 ° C. for 3 hours. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC9.

[Polymerization Example 10] PC10
The reaction was carried out by the method shown in Polymerization Example 8 of polycarbonate diol, except that the amount of 1-heptanol was changed to 11.6 g (0.1 mol). By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC10.

[Polymerization Example 11] PC11
The reaction was carried out by the method shown in Polymerization Example 2 of polycarbonate diol, except that 10.5 g (0.089 mol) of 1,4-cyclohexanediol was added to the raw material. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC11.

[Polymerization Example 12] PC12
In a 2 L glass flask equipped with a rectification column packed with an ordered packing and a stirrer, 456.5 g (6 mol) of 1,3-propanediol (1,3-PDO), 1,4-butanediol (1 , 4-BDO) 360.5 g (4 mol) and 1053.9 g (11.7 mol) of dimethyl carbonate were stirred and dissolved at 70 ° C., and then 0.10 g of titanium tetrabutoxide was added as a catalyst. Then, it heated and stirred at the temperature of 140-150 degreeC under normal pressure, and was made to react for 7 hours, distilling off the mixture of methanol and dimethyl carbonate to produce | generate. Thereafter, the reaction temperature was 150 ° C. to 190 ° C., the pressure was 10 to 15 kPa, and the reaction was performed for 3 hours while distilling off the mixture of methanol and dimethyl carbonate to be produced. Then, it was made to react at 180 degreeC for 4 hours, reducing pressure gradually to 0.5kPa. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC12.

[Polymerization Example 13] PC13
The amount of 1,3-propanediol (1,3-PDO) was 114.1 g (1.5 mol), and the amount of 1,4-butanediol (1,4-BDO) was 766.0 g (8.5 mol). Except for the above, the reaction was carried out by the method shown in Polymerization Example 2 for polycarbonate diol. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC13.

[Polymerization Example 14] PC14
In a 2 L glass flask equipped with a rectification column packed with a regular packing and a stirrer, 385 g (3.7 mol) of 1,5-pentanediol (1,5-PDO) and 1,6-hexanediol (1 , 6-HDO) and 385 g (3.26 mol) of dimethyl carbonate and 1053.9 g (11.7 mol) of dimethyl carbonate were stirred and dissolved at 70 ° C., and then 0.10 g of titanium tetrabutoxide was added as a catalyst. Then, it heated and stirred at the temperature of 140-150 degreeC under normal pressure, and was made to react for 7 hours, distilling off the mixture of methanol and dimethyl carbonate to produce | generate. Thereafter, the reaction temperature was 150 ° C. to 190 ° C., the pressure was 10 to 15 kPa, and the reaction was performed for 3 hours while distilling off the mixture of ethylene glycol and ethylene carbonate to be produced. Then, it was made to react at 210 degreeC for 2 hours, reducing pressure gradually to 0.5kPa. By this reaction, a viscous liquid was obtained at room temperature. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC14.

[Example 1]
44.6 g of isophorone diisocyanate was placed in a 1000 mL four-necked flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube, and a thermometer. Nitrogen was introduced into the flask in an amount of 0.1 cc / min, heated to 50 ° C. using an oil bath with stirring, 0.05 g of dibutyltin dilaurate was added as a catalyst, and 200 g of polycarbonate diol PC1 using a dropping funnel. And a mixed solution of 98.7 g of n-butyl acetate was added dropwise over 1 hour, and the mixture was further stirred for 3 hours to be reacted. The reaction solution was titrated, and it was confirmed by comparing with the calculated amount of isocyanate groups whether all the molecular ends of PC1 at that time were all isocyanate groups. As a result of the titration, it was determined that all of the terminals were isocyanate groups. Therefore, after heating the reaction solution to 70 ° C., nitrogen inflow was stopped, 59.6 g of pentaerythritol triacrylate (70% triester content), hydroquinone monomethyl ether A solution in which 0.02 g was uniformly mixed was dropped over another hour using another dropping funnel, and the mixture was further stirred for 5 hours to be reacted. It was confirmed by titrating the amount of residual isocyanate that the reaction rate of isocyanate was 99% or more. This urethane acrylate is referred to as PUA1.

  For evaluation of the obtained urethane acrylate, 1.5 g of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator was blended with 50 g of the urethane acrylate to prepare a photopolymerization curable composition. Table 2 shows the properties and evaluation results.

[Examples 2 to 6]
A urethane acrylate and a photopolymerizable curable composition were prepared in the same manner as in Example 1 except that polycarbonate diols PC2, PC3, PC4, PC5, and PC6 were used instead of the polycarbonate diol PC1 of Example 1. The obtained urethane acrylates are referred to as PUA2, PUA3, PUA4, PUA5, and PUA6, respectively. Table 2 shows the properties and evaluation results.

[Example 7]
A urethane acrylate and a photopolymerizable curable composition were prepared in the same manner as in Example 1 except that polycarbonate diol PC7 was used instead of polycarbonate diol PC1 of Example 1 and the amount of PC7 charged was 100 g. The resulting urethane acrylate is referred to as PUA7. Table 2 shows the properties and evaluation results.

[Examples 8 to 12]
A urethane acrylate and a photopolymerizable curable composition were prepared in the same manner as in Example 1 except that polycarbonate diols PC8, PC9, PC10, PC11, and PC12 were used in place of the polycarbonate diol PC1 of Example 1. The obtained urethane acrylates are referred to as PUA8, PUA9, PUA10, PUA11, and PUA12, respectively. Table 2 shows the properties and evaluation results.

[Example 13]
44.6 g of isophorone diisocyanate was placed in a 1000 mL four-necked flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube, and a thermometer. Nitrogen was introduced into the flask at a rate of 0.1 cc / min, heated to 50 ° C. using an oil bath with stirring, 0.05 g of dibutyltin dilaurate was added as a catalyst, and 200 g of polycarbonate diol PC2 was added using a dropping funnel. And a mixed solution of 98.7 g of n-butyl acetate was added dropwise over 1 hour, and the mixture was further stirred for 3 hours to be reacted. The reaction solution was titrated, and it was confirmed by comparing with the calculated amount of isocyanate groups whether all the molecular ends of PC1 at that time were all isocyanate groups. As a result of the titration, it was judged that all ends were isocyanate groups. Therefore, after heating the reaction solution to 70 ° C., nitrogen inflow was stopped and 2-hydroxyethyl acrylate 23.2 g and hydroquinone monomethyl ether 0.02 g were mixed uniformly. The solution was added dropwise using another dropping funnel over 1 hour, and further stirred for 5 hours to be reacted. It was confirmed by titrating the amount of residual isocyanate that the reaction rate of isocyanate was 99% or more. This urethane acrylate is referred to as PUA13.

  For evaluation of the obtained urethane acrylate, 1.5 g of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator was blended with 50 g of the urethane acrylate to prepare a photopolymerization curable composition. Table 2 shows the properties and evaluation results.

[Example 14]
44.6 g of isophorone diisocyanate was placed in a 1000 mL four-necked flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube, and a thermometer. Nitrogen was introduced into the flask at a rate of 0.1 cc / min, heated to 50 ° C. using an oil bath with stirring, 0.05 g of dibutyltin dilaurate was added as a catalyst, and 200 g of polycarbonate diol PC2 was added using a dropping funnel. And a mixed solution of 98.7 g of n-butyl acetate was added dropwise over 1 hour, and the mixture was further stirred for 3 hours to be reacted. The reaction solution was titrated, and it was confirmed by comparing with the calculated amount of isocyanate groups whether all the molecular ends of PC1 at that time were all isocyanate groups. As a result of the titration, it was determined that all of the terminals were isocyanate groups. Therefore, after the reaction solution was heated to 70 ° C., the nitrogen inflow was stopped, and pentaerythritol triacrylate (triester content 70%) 45.8 g, 4-pentene A solution in which 6.08 g of -1-ol and 0.02 g of hydroquinone monomethyl ether were uniformly mixed was added dropwise over another hour using another dropping funnel, and further stirred for 5 hours to be reacted. It was confirmed by titrating the amount of residual isocyanate that the reaction rate of isocyanate was 99% or more. This urethane acrylate is referred to as PUA14.

  For evaluation of the obtained urethane acrylate, 1.5 g of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator was blended with 50 g of the urethane acrylate to prepare a photopolymerization curable composition. Table 2 shows the properties and evaluation results.

[Comparative Examples 1-2]
A urethane acrylate and a photopolymerizable curable composition were prepared in the same manner as in Example 1 except that polycarbonate diols PC13 and PC14 were used instead of the polycarbonate diol PC1 of Example 1. The obtained urethane acrylates are referred to as PUA15 and PUA16, respectively. Table 2 shows the properties and evaluation results.

[Example 15]
80 g of PUA1 prepared in Example 1, 40 g of trimethylolpropane triacrylate (TMPTA), 19 g of n-butyl acetate, 0.5 g of leveling agent BYK-331 (manufactured by BYK Chemical), 1-hydroxy 4 g of cyclohexyl phenyl ketone was added and mixed and stirred to obtain a photopolymerization curable coating composition. After coating this on an acrylonitrile-butadiene-styrene (ABS) resin plate, UV photopolymerization was performed with an energy of 1000 mJ / W using a UV irradiator (Oak Manufacturing Co., Ltd., Handy UV-300), and a coating having a thickness of 35 μm was applied. A film was obtained. After being allowed to stand at room temperature for 24 hours, various evaluations were performed. The results are shown in Table 3.

[Examples 16 to 26, Comparative Examples 3 and 4]
Instead of PUA1, PUA2, PUA3, PUA4, PUA5, PUA6, PUA7, PUA8, PUA9, PUA10, PUA11, PUA12, PUA13, PUA14, PUA15, and PUA16 are used in the same manner as in Example 13. Produced. The results of the various evaluations are shown in Table 3.

Claims (6)

It is a reaction product of an isocyanate compound having two or more isocyanate groups in one molecule, a polycarbonate diol, and a hydroxyl group-containing (meth) acrylate having one or more (meth) acryloyl groups in one molecule,
The polycarbonate diol has a structural unit represented by the following formula (1) and a terminal hydroxyl group,
The structural unit represented by the formula (1) contains 20 mol% or more and 90 mol% or less of the structural unit represented by the following formula (2) with respect to the total amount of the structural unit.
Urethane (meth) acrylate.

(In the formula, R ₁ represents a divalent aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 20 carbon atoms.)

In the monomer mixture obtained by alkali hydrolysis of the urethane (meth) acrylate, the content of the allyl alcohol compound represented by the following formula (3) is 0.01% or more with respect to the total amount of the monomer mixture. 3.0% or less,
The urethane (meth) acrylate according to claim 1.
_{CH 2 = CH-R 2 -OH} (3)
(In the formula, R ₂ represents a divalent aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 20 carbon atoms.) The polycarbonate diol contains 0.3% or more and 5.0% or less of a terminal vinyl group based on the total amount of terminal groups.
The urethane (meth) acrylate according to claim 1 or 2. The polycarbonate diol contains 95.0% or more and 99.5% or less of primary terminal hydroxyl groups with respect to the total amount of terminal groups, and has a number average molecular weight of 300 or more and 5000 or less.
The urethane (meth) acrylate as described in any one of Claims 1-3. The isocyanate compound is one or more selected from the group consisting of an aliphatic diisocyanate compound and an alicyclic diisocyanate compound.
The urethane (meth) acrylate as described in any one of Claims 1-4. Containing the urethane (meth) acrylate according to any one of claims 1 to 5,
Curable composition.