JP5691348B2 - Active energy ray-curable polymer composition, cured film of the composition, and laminate having the cured film - Google Patents

Description

  The present invention relates to an active energy ray-curable polymer composition containing a urethane (meth) acrylate-based oligomer, a cured film obtained by irradiating the composition with active energy rays, and a laminate using the same.

  For the purpose of protecting the surface of the substrate and maintaining the appearance, coating with a paint is generally performed. As such paints, paints that are cured by irradiation with energy rays have been developed and put into practical use from the viewpoint of improving the working environment and preventing danger to fire. As such an active energy ray-curable coating material, for example, energy containing urethane acrylate obtained by reacting organic polyisocyanate, polycarbonate polyol, and (meth) acrylate containing one or more hydroxyl groups in the molecule. A linear curable resin composition is known (for example, refer to Patent Document 1).

  Such paints are required to have various properties depending on the application, but the coating properties of the composition, the abrasion resistance, hardness, and mechanical strength of the resulting cured film are the same in any application. Very important.

JP 2009-227915 A

An object of the present invention is to provide an active energy ray-curable polymer composition that provides a cured film having good coatability and excellent wear resistance, hardness, and mechanical strength.
Another object of the present invention is to provide a cured film made of the active energy ray-curable polymer composition and a laminate having the cured film.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have an active energy ray-curable polymer composition containing a urethane (meth) acrylate oligomer obtained using a polycarbonate diol having a specific structure, When the solution viscosity is low and the coatability and workability are excellent, and when this is cured to obtain a cured film, a cured film that is particularly superior in abrasion resistance, hardness, and mechanical strength is obtained. As a result, the present invention has been found.

That is, the present invention is an active energy ray curing containing a urethane (meth) acrylate oligomer which is a reaction product of a raw material containing (1) polyisocyanate, (2) polycarbonate diol, and (3) hydroxyalkyl (meth) acrylate. In the functional polymer composition, the (2) polycarbonate diol is produced by a transesterification reaction between a diol compound giving a repeating unit represented by the following formula (A) and the following formula (B) and a diaryl carbonate. there are, and provides the following condition (i) ~ active energy ray-curable polymer composition characterized by comprising at least a polycarbonate diol satisfying (iii).

(I) A repeating unit represented by the following formula (A) (hereinafter simply referred to as (A)) and a repeating unit represented by the following formula (B) having a structure other than (A) (hereinafter simply referred to as (B) )), Having hydroxyl groups at both ends of the polymer chain, and the ratio of (A) and (B) contained in the polymer is (A) / (B) = 99/1 to 1/99 in molar ratio. is there.
(Ii) The number average molecular weight is 500 or more and 10,000 or less.
(Iii) The following formula (a) is satisfied.
{(Number of moles of (A) at the polymer terminal) / (sum of the number of moles of (A) at the polymer terminal and the number of moles of (B))} / {(number of moles of (A) in the polymer) / (polymer The sum of the number of moles of (A) and the number of moles of (B))}> 1.2 (a)

(In the above formula, n is 0 or 1. R ₁ and R ₂ are each independently selected from the group consisting of alkyl groups, aryl groups, alkenyl groups, alkynyl groups, and alkoxy groups having 1 to 15 carbon atoms. And may have an oxygen atom, a sulfur atom, a nitrogen atom, a halogen atom or a substituent containing these in the range of the carbon number, and X and Y each independently contain a hetero atom. Represents a good divalent group having 1 to 20 carbon atoms.)

  Moreover, this invention provides the said active energy ray-curable polymer composition whose molecular weight between calculation network crosslinking points is 500-10,000.

  Furthermore, the present invention provides the active energy ray-curable polymer composition, wherein the raw material further contains a high molecular weight polyol having a number average molecular weight of 500 or more other than polycarbonate diol satisfying the conditions (i) to (iii). .

  Furthermore, the present invention provides the active energy ray-curable polymer composition, wherein the raw material further contains a low molecular weight polyol having a number average molecular weight of less than 500 excluding the polycarbonate diol.

  Furthermore, the present invention has a structure in which the urethane (meth) acrylate oligomer has a structure in which a urethane prepolymer having an isocyanate group at a terminal and the (3) hydroxyalkyl (meth) acrylate are reacted by a urethane bond, The urethane prepolymer provides the active energy ray-curable polymer composition obtained by polymerizing the (1) polyisocyanate and the (2) polycarbonate diol with a urethane bond.

  The present invention also provides a cured film obtained by irradiating the active energy ray-curable polymer composition with active energy rays.

  Furthermore, this invention provides the laminated body which has a layer which consists of said cured film on a base material.

  Since the active energy ray-curable polymer composition of the present invention contains a urethane (meth) acrylate oligomer that is a reaction product of a raw material containing polycarbonate diol that satisfies the above-mentioned specific conditions as polycarbonate diol, solution viscosity In addition to being excellent in workability and coating property, when cured to form a cured film, a cured film having excellent wear resistance, hardness and mechanical strength can be formed.

  Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is a representative example of the embodiments of the present invention, and the present invention is not limited to these contents. .

In the present specification, (meth) acrylate is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The same applies to (meth) acryloyl and (meth) acryl.
Further, in the present specification, “to” is used in the sense of including the numerical values described before and after it as a lower limit value and an upper limit value.

  In addition, the method for measuring or calculating the molecular weight or number average molecular weight of the raw material compound of urethane (meth) acrylate oligomer such as polycarbonate diol according to the present invention is as follows.

  For compounds other than polyols having a molecular weight distribution in a gel permeation chromatogram (hereinafter abbreviated as GPC), the molecular weight can be calculated from the chemical formula, and the number average molecular weight can be determined by GPC as follows.

<Calculation of number average molecular weight by GPC>
Using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation), tetrahydrofuran (THF) as a solvent, polystyrene as a standard sample, TSK gel superH1000 + H2000 + H3000 as a column, liquid feeding speed 0.5 mL / min, column oven temperature 40 The number average molecular weight is measured at ° C.

  Moreover, about the polyol which has molecular weight distribution by GPC, the number average molecular weight can be calculated | required as follows by OH value.

<Calculation of number average molecular weight of polyol by OH number>
Into an Erlenmeyer flask, 2 g of polyol and 0.5 mol / L phthalic anhydride pyridine solution are added, reacted at 100 ° C. for 2 hours, and then diluted with 150 mL of acetone. Then, it titrates with 0.5 mol / L sodium hydroxide aqueous solution. Further, a titration is performed in the same manner except that no polyol is added to the Erlenmeyer flask to obtain a blank. And OH value and a number average molecular weight are computed by the following formula | equation.
OH value = {(BA) × 0.5 × 56.11 × 1000} / 2 × 1000
A: Amount of aqueous sodium hydroxide solution required for titration of polyol-containing solution B: Amount of aqueous sodium hydroxide solution required for titration of blank solution not containing polyol Number average molecular weight of polyol = {(56.11 × 1000) / OH value} × number of functional groups In the above formula, the “number of functional groups” is the number of OH groups contained in one molecule of polyol.

  Moreover, about the isocyanate which has molecular weight distribution by GPC, the number average molecular weight can be calculated | required as follows by NCO%.

<Calculation of the number average molecular weight of polyisocyanate by NCO%>
Into an Erlenmeyer flask, 1 g of polyisocyanate and 20 mL of a 0.5 mol / L dibutylamine toluene solution are added, diluted with 100 mL of acetone, and reacted at 25 ° C. for 30 minutes. Thereafter, the solution is titrated with a 0.5 mol / liter hydrochloric acid aqueous solution. Moreover, titration is performed similarly except polyisocyanate was not put into the Erlenmeyer flask, and a blank is obtained. And NCO% and a number average molecular weight are computed by the following formula | equation.
NCO% = {(B1-A1) × 0.5 × 42.02} / (1 × 1000) × 100
A1: Amount of hydrochloric acid aqueous solution required for titration of polyisocyanate-containing solution (mL)
B1: Amount of hydrochloric acid aqueous solution required for titration of blank solution containing no polyisocyanate (mL)
Number average molecular weight of polyisocyanate = (42.02 / NCO%) × number of NCO groups contained in one molecule of polyisocyanate

The active energy ray-curable polymer composition of the present invention contains a urethane (meth) acrylate oligomer.
The urethane (meth) acrylate oligomer used in the present invention is a compound having one or more radically polymerizable (meth) acryloyl groups and at least two urethane bonds in the molecule. Urethane (meth) acrylate oligomer is a cured product by irradiation with active energy rays, has a balanced tensile strength and excellent tensile elongation, and is excellent in surface curability as a composition, so that tack remains less. Thus, it is superior to other typical active energy ray-curable oligomers such as epoxy (meth) acrylate oligomers and acrylic (meth) acrylate oligomers.

  The urethane (meth) acrylate oligomer in the present invention (hereinafter referred to as “the urethane (meth) acrylate oligomer of the present invention”) is composed of (1) polyisocyanate, (2) polycarbonate diol, and (3) hydroxyalkyl (meta ) A reaction product of a raw material containing acrylate. The urethane (meth) acrylate oligomer contained in the active energy ray-curable polymer composition of the present invention may be one type or two or more types.

[Raw compound of urethane (meth) acrylate oligomer]
Below, the raw material compound of the urethane (meth) acrylate-type oligomer of this invention is demonstrated.

(1) Polyisocyanate (1) Polyisocyanate as a raw material compound for producing the urethane (meth) acrylate oligomer in the present invention is one of substituents containing two or more isocyanate groups and isocyanate groups in one molecule. Alternatively, it is a compound having both (also referred to as “isocyanate groups”). (1) One type of polyisocyanate may be used, or two or more types may be used. Moreover, in 1 type of polyisocyanate, isocyanate groups may be the same and may differ.

  As a substituent containing an isocyanate group, a C1-C5 alkyl group, an alkenyl group, or an alkoxyl group containing one or more isocyanate groups is mentioned, for example. The number of carbon atoms of the alkyl group or the like as a substituent containing an isocyanate group is more preferably 1 to 3.

  (1) The number average molecular weight of the polyisocyanate is preferably 100 or more from the viewpoint of the balance between strength and elastic modulus as a cured product obtained by curing the active energy ray-curable polymer composition, and 150 More preferably, it is 1,000 or less, more preferably 500 or less.

  The number average molecular weight of the polyisocyanate is obtained from a calculated value from a chemical formula in the case of a polyisocyanate composed of a single monomer, or a calculated value from NCO% in the case of a polyisocyanate composed of two or more monomers. be able to.

  Examples of the polyisocyanate include aliphatic polyisocyanates, polyisocyanates having an alicyclic structure, and aromatic polyisocyanates.

  An aliphatic polyisocyanate is a compound having an aliphatic structure and two or more isocyanate groups bonded thereto. An aliphatic polyisocyanate is preferable from the viewpoint of enhancing the weather resistance of a cured product obtained by curing the active energy ray-curable polymer composition and imparting flexibility. The aliphatic structure in the aliphatic polyisocyanate is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 6 carbon atoms. Examples of such aliphatic polyisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate, and aliphatic triisocyanates such as tris (isocyanatohexyl) isocyanurate. Be mentioned

  The polyisocyanate preferably contains a polyisocyanate having an alicyclic structure from the viewpoint of mechanical strength and stain resistance of a cured product obtained by curing the active energy ray-curable polymer composition of the present invention.

  The polyisocyanate having an alicyclic structure is a compound having an alicyclic structure and two or more isocyanate groups bonded thereto. The alicyclic structure in the polyisocyanate having an alicyclic structure is not particularly limited, but is preferably a cycloalkylene group having 3 to 6 carbon atoms. Examples of the polyisocyanate having an alicyclic structure include diisocyanates having an alicyclic structure such as bis (isocyanate methyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate, and tris (isocyanate isophorone) isocyanate. Examples thereof include triisocyanates having an alicyclic structure such as nurate.

  The polyisocyanate having an alicyclic structure is also preferable from the viewpoint of enhancing the weather resistance of a cured product obtained by curing the active energy ray-curable polymer composition. As the polyisocyanate having such an alicyclic structure, , For example, bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate.

  An aromatic polyisocyanate is a compound having an aromatic structure and two or more isocyanate groups bonded thereto. Although the aromatic structure in aromatic polyisocyanate is not specifically limited, It is preferable that it is a C6-C13 bivalent aromatic group. Examples of such aromatic polyisocyanates include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and naphthalene diisocyanate.

  The aromatic polyisocyanate is preferable from the viewpoint of increasing the mechanical strength of a cured product obtained by curing the active energy ray-curable polymer composition. Examples of such aromatic polyisocyanate include tolylene diisocyanate and diphenylmethane diisocyanate. Is mentioned.

(2) Polycarbonate diol (2) Polycarbonate diol as a raw material compound constituting the urethane (meth) acrylate oligomer of the present invention is a polycarbonate diol that satisfies at least the following conditions (i) to (iii) (hereinafter, this polycarbonate diol) May be referred to as "specific polycarbonate diol").

(I) A repeating unit represented by the following formula (A) (hereinafter simply referred to as (A)) and a repeating unit represented by the following formula (B) having a structure other than (A) (hereinafter simply referred to as (B) )), Having hydroxyl groups at both ends of the polymer chain, and the ratio of (A) and (B) contained in the polymer is (A) / (B) = 99/1 to 1/99 in molar ratio. is there.
(Ii) The number average molecular weight is 500 or more and 10,000 or less.
(Iii) The following formula (a) is satisfied.
{(Number of moles of (A) at the polymer terminal) / (sum of the number of moles of (A) at the polymer terminal and the number of moles of (B))} / {(number of moles of (A) in the polymer) / (polymer The sum of the number of moles of (A) and the number of moles of (B))}> 1.2 (a)

(In the above formula, n is 0 or 1. R ₁ and R ₂ are each independently selected from the group consisting of alkyl groups, aryl groups, alkenyl groups, alkynyl groups, and alkoxy groups having 1 to 15 carbon atoms. And may have an oxygen atom, a sulfur atom, a nitrogen atom, a halogen atom or a substituent containing these in the range of the carbon number, and X and Y each independently contain a hetero atom. Represents a good divalent group having 1 to 20 carbon atoms.)

  1 type of specific polycarbonate diol may be used and 2 or more types may be used.

In the above formula (A), R ₁ and R ₂ may be independently different groups or the same group. The number of carbon atoms of these substituents needs to be 1 or more in order to bring about the effect of the present invention. However, if the number of carbon atoms is too large, problems such as a decrease in polymerization reactivity occur, so the number is 15 or less, preferably 10 or less.

  Examples of the alkyl group include methyl group, ethyl group, i-propyl group, n-propyl group, n-butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl group etc. are mentioned, A methyl group, an ethyl group, n-propyl group, n-butyl group, a pentyl group etc. are more preferable.

  Examples of the aryl group include a phenyl group, a naphthyl group, a benzyl group, a tolyl group, and an o-xylyl group.

  Examples of the alkenyl group include a vinyl group (ethylenyl), a propenyl group, a butenyl group, and a pentenyl group, and a vinyl group and a propenyl group are particularly preferable.

As said alkynyl group, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group etc. are mentioned, for example, An ethynyl group, a propynyl group, etc. are more preferable.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and an n-butoxy group, and among them, a methoxy group, an ethoxy group, an n-propoxy group, and the like are more preferable.

  Examples of the ring group which may be further substituted with these alkyl group, aryl group, alkenyl group, alkynyl group and alkoxy group include nitrile group, nitro group, amino group, amide group, methoxy group, ethoxy group, n -A propoxy group, an i-propoxy group, an n-butoxy group, a mercapto group, a halogen atom, etc. are mentioned, A nitro group, a halogen atom, etc. are more preferable. Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

In the formula (A), n is preferably 0, and R ₁ and R ₂ are each independently preferably an alkyl group having 1 to 5 carbon atoms in terms of the properties of the polycarbonate diol.

  In the above formulas (A) and (B), X and Y are not particularly limited in obtaining the effects of the present invention, and may be any structure of a chain group or a cyclic group. Carbon number as an element constituting these groups is 1 or more and 20 or less, preferably 15 or less, more preferably 10 or less, and may contain a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom.

  Y is a divalent group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms not containing a quaternary carbon atom, or a carbon atom bonded to at least oxygen and a carbon atom bonded to the carbon atom in Y. A divalent group having 5 to 20 carbon atoms, preferably 5 to 15 carbon atoms, which is not a quaternary carbon atom is preferable.

Specific examples of X _{groups, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 -, - CH 2 CH (CH 3) Examples include CH ₂ —, a group represented by the following formula (C), and the like, and —CH ₂ —, —CH ₂ CH ₂ —, and a group represented by the following formula (C) are more preferable.

  As a specific example of the group of Y, a group generated from the exemplified compound described later is preferable as the diol compound giving the structure of the formula (B), and more preferable examples of the diol compound giving the structure of (B) are preferable. Examples include groups generated from compounds.

  The specific polycarbonate diol has a structure in which both terminal groups are hydroxyl groups, and this hydroxyl group can react with isocyanate during the urethanization reaction.

  The ratio of (A) and (B) constituting the specific polycarbonate diol is (A) / (B) = 99/1 to 1/99 in molar ratio. The effect of the present invention is the (A) structure, and if the proportion of the (A) structure is too small, the effect may not be sufficiently obtained. On the other hand, if it is too large, the handleability during polymerization is poor. There is a case. The ratio of (A) and (B) contained in the specific polycarbonate diol is preferably (A) / (B) = 80/20 to 20/80 in terms of molar ratio, and moreover, (A) / (B) = 70/30 to 30/70 is more preferable.

  The specific polycarbonate diol further satisfies the following formula (A) (hereinafter, the value calculated by the following formula is referred to as “terminal (A) ratio”).

{(Number of moles of (A) at the polymer terminal) / (sum of the number of moles of (A) at the polymer terminal and the number of moles of (B))} / {(number of moles of (A) in the polymer) / (polymer The sum of the number of moles of (A) and the number of moles of (B))}> 1.2 (a)

That is, the specific polycarbonate diol has a feature that “the ratio of the monomer constituting the terminal of the polymer chain is larger in (A) than in (B)”. The polycarbonate diol having such a structure is characterized by being easily liquid and having a low viscosity and being easy to handle. Moreover, the cured film obtained from the urethane (meth) acrylate oligomer produced using this specific polycarbonate diol maintains the heat resistance, weather resistance, and water resistance, which are characteristics as a polyurethane derived from the conventional polycarbonate diol. It exhibits the characteristics of being excellent in flexibility and elastic recovery, flexibility and flexibility at low temperatures. Although details of the reason why such characteristic physical properties are obtained are not clear, R ₁ , such as a dialkyl substituent derived from (A) of the specific polycarbonate diol, at a site close to the hard segment of the obtained polyurethane. It is presumed that the presence of the R ₂ substituent effectively suppresses hard segment stacking and, as a result, expresses the flexibility of polyurethane and achieves desired physical properties.

In order to effectively obtain the above effect, the terminal (A) ratio is larger than 1.2, preferably 1.3 or more, more preferably 1.4 or more.
The upper limit of the terminal (A) ratio is not particularly limited, but is 200, preferably 100, and more preferably 50 as a practically manufacturable range.

The method for measuring the abundance ratio of each structure for calculating the terminal (A) ratio is not particularly limited as long as the abundance ratio can be obtained. For example, it is easy from the integrated value of the ¹ H-NMR signal of polycarbonate diol. Can be requested.

  The number average molecular weight of the specific polycarbonate diol is good workability due to the appropriate viscosity of the urethane (meth) acrylate oligomer obtained, and the mechanical strength of the cured product obtained by curing the active energy ray-curable polymer composition And from a viewpoint of abrasion resistance, it is 500 or more and 10,000 or less. The number average molecular weight of the specific polycarbonate diol is preferably 5,000 or less and more preferably 3,000 or less from the above viewpoint. Further, the number average molecular weight of the specific polycarbonate diol is preferably 700 or more, more preferably 1,000 or more from the above viewpoint. When the number average molecular weight of the specific polycarbonate diol is reduced, the workability is improved and the mechanical strength and wear resistance tend to be improved. When the number average molecular weight of the specific polycarbonate diol increases, the flexibility that can follow the deformation during the three-dimensional processing of the cured product tends to decrease.

  The lower limit of the hydroxyl value of the specific polycarbonate diol is preferably 10 mg-KOH / g, more preferably 20 mg-KOH / g, and still more preferably 35 mg-KOH / g. The upper limit is preferably 230 mg-KOH / g, more preferably 160 mg-KOH / g, and still more preferably 130 mg-KOH / g. If the hydroxyl value is less than the above lower limit, the viscosity may be too high and handling during urethanization may be difficult, and if it exceeds the upper limit, the strength as a urethane resin may be insufficient.

  Further, the lower limit of the molecular weight distribution (Mw / Mn) of the specific polycarbonate diol is preferably 1.5, more preferably 2.0. On the other hand, the upper limit is preferably 3.5, more preferably 3.0. Here, Mw is a weight average molecular weight, and Mn is a number average molecular weight, which can be usually obtained by measurement by gel permeation chromatography.

  When the molecular weight distribution exceeds the above upper limit, the physical properties of the cured film obtained from the urethane (meth) acrylate oligomer produced using the polycarbonate diol tend to be deteriorated, such as being hardened at a low temperature and having poor elongation, If an attempt is made to produce a polycarbonate diol that is less than the above lower limit, a high degree of purification such as removal of the oligomer may be required.

  The polycarbonate diol used in the present invention has a structure in which a diol is polymerized by a carbonate group. However, depending on the manufacturing method, some of the ether structure may be mixed in. If the amount of the compound increases, the ether structure may cause the weather resistance and heat resistance to deteriorate. It is desirable to manufacture so as not to increase. Therefore, the ratio of the ether bond to the carbonate bond contained in the polymer of the specific polycarbonate diol is preferably 2/98 or less, more preferably 1/99 or less, and further preferably 0.5 / 99.5 or less in molar ratio. It is.

  The specific polycarbonate diol is usually in the form of a liquid around room temperature and has a characteristic of excellent handling properties. This is a very advantageous property for the production of polyurethane on an industrial scale and is different from the room-temperature properties of a waxy cloudy solid found in polyhexamethylene carbonate diol, a common grade of polycarbonate diol. Is a point.

  This property of the specific polycarbonate diol can be expressed, for example, by viscosity. The lower limit of the viscosity at 40 ° C. is preferably 0.1 Pa · s, more preferably 1 Pa · s, still more preferably 5 Pa · s, and the upper limit is preferably 200 Pa · s, more preferably 150 Pa · s, still more preferably 100 Pa · s. If the viscosity is too high or too low, handling may be difficult.

  The color tone of the specific polycarbonate diol is preferably in a range that does not affect the color of the resulting polyurethane cured film, and is 100 or less in terms of the degree of coloration expressed by the Hazen color number (hereinafter referred to as “APHA value”). Is more preferable, 50 is more preferable, and 30 is more preferable.

  The production of the specific polycarbonate diol can be carried out by subjecting the raw material diol compound giving the structures (A) and (B) described above and a carbonic acid diester to an ester exchange reaction.

  Specific examples of the raw material monomer diol compound giving the structure (A) and the structure (B) when polycarbonate diol is used are shown below.

  Specific examples of the diol compound that gives the structure (A) include 2,2-dimethyl-1,3-propanediol (neopentyl glycol, which may be abbreviated as “NPG” hereinafter), 2-ethyl. -2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-pentyl-2-propyl-1,3-propanediol, 2-pentyl-2-propyl-1, 2,2-dialkyl-substituted 1,3-propanediols such as 3-propanediol (hereinafter sometimes referred to as “2,2-dialkyl-1,3-propanediols”, provided that the alkyl group is carbon An alkyl group having a number of 15 or less), 2,2,4,4-tetramethyl-1,5-pentanediol, 2,2,9,9-tetramethyl-1,10-decanediol. Tetraalkyl-substituted alkylene diols, diols containing cyclic groups such as 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane 2,2-diphenyl-1,3-propanediol, 2,2-divinyl-1,3-propanediol, 2,2-diethynyl-1,3-propanediol, 2,2-dimethoxy-1,3 -Propanediol, bis (2-hydroxy-1,1-dimethylethyl) ether, bis (2-hydroxy-1,1-dimethylethyl) thioether, 2,2,4,4-tetramethyl-3-cyano-1 , 5-pentanediol and the like. These diols may be used alone or in combination.

Among these, in the structure (A), those in which n is 0 and R ₁ and R ₂ each independently give an alkyl group having 1 to 5 carbon atoms are preferred. Specific compounds giving this structure are 2, 2 -Dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-pentyl-2-propyl Examples include 2,2-dialkyl-1,3-propanediols such as -1,3-propanediol and 2-pentyl-2-propyl-1,3-propanediol.

  Examples of specific diol compounds that give the structure of (B) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,20-eicosanediol, etc. Chain terminal diols, diols having ether groups such as diethylene glycol, triethylene glycol, tetraethylene glycol, polytetramethylene glycol, thioether diols such as bishydroxyethyl thioether, 2-ethyl-1,6-hexanediol 2-methyl-1,3-propanediol Branched diols such as 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4- Cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 1,4-dihydroxyethylcyclohexane, isosorbide, 2,5-bis (hydroxymethyl) tetrahydrofuran, 4, Diols having a cyclic group in the molecule such as 4′-isopropylidenedicyclohexanol and 4,4′-isopropylidenebis (2,2′-hydroxyethoxycyclohexyne), diethanolamine, N-methyldiethanolamine and the like Nitrogen diols, bis (hydroxy And sulfur-containing diols such as ethyl) sulfide. These diols may be used alone or in combination of two or more.

  Specific examples of the combination of the diol compound giving the structure (A) and the diol compound giving the structure (B) include 2,2-dialkyl-1,3-diol as the diol compound giving the structure (A). Propanediol is preferable, 2,2-dimethyl-1,3-propanediol (neopentylglycol) is more preferable, and among the compounds giving the structure of (B) to be combined with these, diols having 20 carbon atoms in particular Or, a diol having an ether group is preferred. Further, ethylene glycol, 1,3-propanediol (neopentyl glycol), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10- Decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, isosorbide are available raw material diols It is more preferable in terms of excellent properties and physical properties. When a urethane (meth) acrylate oligomer is produced using the polycarbonate diol obtained from these, the solution viscosity is low, the handling property is excellent, and the polyurethane of the obtained cured film becomes more flexible.

  On the other hand, examples of the carbonic acid diester that can be used for the production of the specific polycarbonate diol include dialkyl carbonate, diaryl carbonate, and alkylene carbonate. These may use 1 type and may use 2 or more types.

  Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate, and ethyl isobutyl carbonate.

  Examples of diaryl carbonates include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, and the like.

  Examples of alkylene carbonates include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2- Examples include pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, and neopentyl carbonate. It is done.

  Among these, diaryl carbonate is rich in reactivity, the reaction proceeds quickly, and is efficient and preferable for industrial production. In particular, 2,2-dialkyl-1,3-propanediol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane Diol compounds such as these have low reactivity, and to produce polycarbonate diol using dialkyl carbonate or alkylene carbonate, harsher reaction conditions, that is, conditions using a large amount of catalyst and the quality of polycarbonate diol, which is the target product, are degraded. Various conditions are required. Even in such a case, when diaryl carbonate is used, this is superior in reactivity compared to alkyl carbonate, so that the reaction proceeds even under mild conditions even with these less reactive diol compounds. This is preferable.

  Among diaryl carbonates, diphenyl carbonate that can be easily and inexpensively obtained as an industrial raw material is more preferable.

  The lower limit of the amount of these carbonic acid diesters is preferably 0.80, more preferably 0.85, still more preferably 0.90, and the upper limit is preferably 1.10, based on a total of 1 mol of diol compounds. The molar ratio is preferably 1.05, more preferably 1.03.

  In producing the specific polycarbonate diol, a transesterification catalyst may be used to promote polymerization.

  Any metal that can be used as a transesterification catalyst can be used without limitation as long as it is generally considered to have transesterification ability. Examples of such metals include alkali metals such as lithium, sodium, potassium, rubidium and cesium; alkaline earth metals such as magnesium, calcium, strontium and barium; titanium, zirconium, hafnium, cobalt, zinc, aluminum, Examples thereof include transition metals such as germanium, tin, lead, antimony, and bismuth; lanthanide-based metals such as lanthanum, cerium, europium, and ytterbium. These metals may be used as a simple metal or as a metal compound such as a salt. Examples of the metal compound used as a metal compound include chlorides, chlorides, Halides such as bromide and iodide; carboxylates such as acetate, formate and benzoate; sulfonates such as methanesulfonic acid, toluenesulfonic acid and trifluoromethanesulfonic acid; phosphates and hydrogenphosphate, phosphoric acid Phosphorus-containing salts such as dihydrogen salts; acetylacetonate salts; and alkoxides such as methoxide and ethoxide can be used. Preferably, alkali metal, alkaline earth metal, transition metal acetates, halides, and alkoxides are used. These metals and metal compounds may be used alone or in combination of two or more.

  Specific examples of the alkali metal compound of the transesterification catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate. , Cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, phosphorus Disodium hydrogen hydrogen, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium phenol , Potassium salt, cesium salt and lithium salt and the like.

  Examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate , Barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate, and the like.

  Examples of transition metal compounds include titanium alkoxides such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate; titanium halides such as titanium tetrachloride; zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, etc. Zinc salts of: tin compounds such as tin chloride (II), tin chloride (IV), tin acetate (II), tin acetate (IV), dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide; zirconium acetylacetonate, oxyacetic acid Zirconium compounds such as zirconium and zirconium tetrabutoxide; lead compounds such as lead (II) acetate, lead (IV) acetate, lead (IV) chloride and the like.

  The amount of the transesterification catalyst used is preferably an amount that does not affect the performance even if it remains in the obtained polycarbonate diol, and the upper limit as the weight ratio of the metal to the weight of the raw material diol compound is preferably 500 ppm, More preferably, it is 100 ppm, More preferably, it is 50 ppm. On the other hand, the lower limit is an amount that provides sufficient polymerization activity, that is, preferably 0.01 ppm, more preferably 0.1 ppm, and even more preferably 1 ppm.

  The reaction temperature in the transesterification reaction can be arbitrarily adopted as long as a practical reaction rate can be obtained. Usually, the lower limit of the temperature is 70 ° C, preferably 100 ° C, more preferably 130 ° C. If the upper limit of the reaction temperature is too high, the resulting polycarbonate diol may be colored, or quality problems such as the formation of an ether structure may occur. Therefore, the upper limit is usually 250 ° C., preferably 230 ° C., more preferably 200 ° C.

  Furthermore, the reaction temperature is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and even more preferably 160 ° C. or lower throughout the entire ester exchange reaction for producing polycarbonate diol. When all the above steps include a step with a reaction temperature exceeding 170 ° C., it may be easy to color depending on the conditions.

  Although the reaction can be carried out at normal pressure, the transesterification reaction is an equilibrium reaction, and the reaction can be biased toward the production system by distilling off the light-boiling components produced out of the system. Therefore, it is usually preferable to carry out the reaction in the latter half of the reaction while employing a reduced pressure condition while distilling off the light boiling component. Alternatively, the reaction can be carried out while distilling off the light boiling component produced by gradually lowering the pressure from the middle of the reaction. In particular, it is preferable to increase the degree of vacuum at the end of the reaction, because by-produced monoalcohol, phenols, and cyclic carbonate can be distilled off. In this case, the upper limit of the reaction pressure at the end of the reaction is preferably 10 kPa, more preferably 5 kPa, and even more preferably 1 kPa. In order to effectively distill these light-boiling components, the reaction can be performed while an inert gas such as nitrogen, argon or helium is circulated through the reaction system.

  When using a low-boiling carbonate or diol compound as a raw material in the transesterification reaction, the reaction is initially performed near the boiling point of the carbonate or diol compound, and the temperature is gradually raised as the reaction proceeds. Further, a method of further proceeding the reaction can be employed. In this case, the unreacted carbonate ester can be prevented from being distilled off at the initial stage of the reaction, which is preferable. It is also possible to attach a dry distillation tube to the reactor in order to prevent the distillation of these raw materials, and to carry out the reaction while refluxing the carbonate ester and diol compound. Can be accurately matched, which is preferable.

  The polymerization reaction can be carried out batchwise or continuously. In the present invention, the polymerization reaction is preferably carried out continuously from the standpoint of product stability. The apparatus to be used may be any of a tank type, a tube type, or a tower type, and known polymerization tanks equipped with various stirring blades can be used. The atmosphere during the temperature rise of the apparatus is not particularly limited, but it is preferably carried out in an inert gas such as nitrogen gas under normal pressure or reduced pressure from the viewpoint of product quality.

  The polymerization reaction ends when the molecular weight of the polycarbonate diol to be produced is measured while the target molecular weight is reached. The reaction time required for the polymerization cannot be specified unconditionally because it varies greatly depending on whether or not the diol compound, carbonate ester and transesterification catalyst to be used are used, and the type, but is usually 50 hours or less, preferably 20 hours or less. More preferably, it is 10 hours or less.

  When a transesterification catalyst is used in the reaction, the metal of the transesterification catalyst remains in the usually obtained polycarbonate diol. If these metal catalysts remain, the reaction may not be controlled during the urethanization reaction. In order to suppress the influence of this residual catalyst, a known deactivator, for example, a phosphorus compound, may be added in an amount equivalent to that of the transesterification catalyst used. Furthermore, the transesterification catalyst can be inactivated efficiently by treating at a temperature of 60 to 150 ° C., preferably 90 to 120 ° C. after the addition.

  Examples of phosphorus compounds used for inactivating the transesterification catalyst include inorganic phosphoric acid such as phosphoric acid and phosphorous acid, and dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, And organic phosphate esters such as triphenyl phosphate.

  As described above, the amount of the phosphorus compound used may be approximately equimolar to the transesterification catalyst used. Specifically, the upper limit is preferably 5 with respect to 1 mol of the transesterification catalyst used. Mol, more preferably 2 mol, and the lower limit is preferably 0.8 mol, more preferably 1.0 mol. When a smaller amount of phosphorus compound is used, the transesterification catalyst in the reaction product is not sufficiently deactivated, and the obtained polycarbonate diol is used for producing the urethane (meth) acrylate oligomer of the present invention. When used as a raw material, the reactivity of the polycarbonate diol with respect to the isocyanate group may not be sufficiently lowered. Further, when a phosphorus compound exceeding this range is used, the obtained polycarbonate diol may be colored.

  The inactivation of the transesterification catalyst by adding a phosphorus compound can be performed at room temperature, but it is more efficient when heat-treated. The upper limit of the temperature of this heat treatment is preferably 150 ° C., more preferably 120 ° C., still more preferably 100 ° C., and the lower limit is preferably 50 ° C., more preferably 60 ° C., and further preferably 70 ° C. When the temperature is lower than this, it takes time to deactivate the transesterification catalyst, which is not efficient and the degree of deactivation may be insufficient. On the other hand, at a temperature exceeding 150 ° C., the obtained polycarbonate diol may be colored.

  The time for reacting with the phosphorus compound is not particularly limited, but is usually 1 to 5 hours.

  The polycarbonate diol product thus obtained may contain a cyclic carbonate by-produced during production. For example, when 2,2-dialkyl-1,3-propanediol is used as the raw material diol compound, 5,5-dialkyl-1,3-dioxan-2-one, or two or more of them are cyclic. In some cases, the product is formed as a cyclic compound. In particular, when 2,2-dimethyl-1,3-propanediol (neopentyl glycol) is used as the starting diol compound, 5,5-dimethyl-1,3-dioxan-2-one (neopentyl carbonate) In addition, there may be cases where two or more of these molecules form a cyclic compound as a cyclic compound. Since these compounds are undesirable impurities that may cause side reactions in the urethanization reaction, it is desirable to remove them as much as possible in the production stage. The content of these impurities contained in the polycarbonate diol product is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

  As described above, diaryl carbonate is preferable as the carbonic acid diester used in the production of the polycarbonate diol. However, when diaryl carbonate is used, hydroxyaryl derived from diaryl carbonate (hereinafter sometimes abbreviated as “phenols”) is secondary. Care must be taken not to leave a large amount in the polycarbonate diol product. If the residual amount of phenols is large, the phenols are monofunctional compounds, which can be a polymerization inhibitor during polyurethane formation and are also irritating substances, which is not preferable. The content of phenols contained in the polycarbonate diol product is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and still more preferably 0.005% by mass or less.

  Further, the residual amount of the raw material diol compound used in the production of the polycarbonate diol product is preferably 1% by mass or less, more preferably 0.1% by mass or less, and further preferably 0.05% by mass or less. It is. When the residual amount of the raw material diol compound is large, the molecular length of the soft segment portion when urethane is used may be insufficient.

  The specific polycarbonate diol basically has a hydroxyl group at the polymer terminal. However, some of the polycarbonate diol products may not have a hydroxyl group at the polymer end as impurities. In this case, the proportion of impurities having no hydroxyl group at the polymer terminal contained in the polycarbonate diol product is preferably 5 mol% or less, more preferably 3 mol of the total number of terminal groups as the number of terminal groups having no hydroxyl group. % Or less, more preferably 1 mol% or less. When the ratio of the terminal group which does not have a hydroxyl group is large, problems such as an increase in the degree of polymerization may not occur during the urethanization reaction, which is not preferable. Examples of the terminal structure having no hydroxyl group include phenoxycarbonyl, methoxycarbonyl, ethoxycarbonyl, and olefin, depending on the production method.

  In addition, as described above, when a transesterification catalyst is used during the production of polycarbonate diol, the catalyst may remain in the resulting polycarbonate diol product, but if too much catalyst remains, a urethanization reaction is assumed. The above may be promoted, which is not preferable. The amount of catalyst remaining in the polycarbonate diol product is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less as the content of the catalyst metal.

  From the above, impurities that do not have a hydroxyl group at the polymer end in the polycarbonate diol product obtained by the reaction, phenols, raw material diol compounds and carbonates, by-product light-boiling cyclic carbonates, and added esters Purification can be performed for the purpose of removing the exchange catalyst and the like. In the purification at that time, a method of distilling off a light boiling compound by distillation can be employed. As a specific method of distillation, there is no particular limitation on the form such as vacuum distillation, steam distillation, thin film distillation, etc., and any method can be adopted, but thin film distillation is particularly effective. The thin film distillation conditions are not particularly limited, but the upper limit of the temperature during thin film distillation is preferably 250 ° C., more preferably 200 ° C., and the lower limit is preferably 120 ° C., more preferably 150 ° C. When the temperature is lower than 120 ° C., the effect of removing light boiling components may be reduced. On the other hand, when the temperature is higher than 250 ° C., the polycarbonate diol obtained after thin film distillation may be colored. The upper limit of the pressure during thin film distillation is preferably 500 Pa, more preferably 150 Pa, and even more preferably 50 Pa. When the pressure is higher than this, the effect of removing light boiling components may be reduced. Further, the temperature of the polycarbonate diol that is kept immediately before the thin-film distillation has an upper limit of preferably 250 ° C., more preferably 150 ° C., and a lower limit of preferably 80 ° C., more preferably 120 ° C. When the temperature is lower than 80 ° C., the fluidity of the polycarbonate diol immediately before the thin film distillation may decrease. On the other hand, when the temperature is higher than 250 ° C., the polycarbonate diol obtained after thin film distillation may be colored. Further, in order to remove water-soluble impurities, it may be washed with water, alkaline water, acidic water, a chelating agent solution or the like. In that case, the compound to be dissolved in water can be arbitrarily selected.

(3) Hydroxyalkyl (meth) acrylate (3) Hydroxyalkyl (meth) acrylate as a raw material compound for producing the urethane (meth) acrylate oligomer in the present invention is composed of one or more hydroxyl groups and one or more (meth). It is a compound having an acryloyl group and preferably a hydrocarbon group having 1 to 30 carbon atoms. (3) One kind of hydroxyalkyl (meth) acrylate may be used, or two or more kinds thereof may be used.

  (3) As hydroxyalkyl (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, Cyclohexanedimethanol mono (meth) acrylate, addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, addition reaction product of 4-hydroxybutyl (meth) acrylate and caprolactone, glycidyl ether and (meth) acrylic acid Addition reaction products, glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

  Among the above, the number of carbon atoms is 2 to 4 between the (meth) acryloyl group and the hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. A hydroxyalkyl (meth) acrylate having an alkylene group is particularly preferred from the viewpoint of the mechanical strength of the resulting cured film.

  (3) The molecular weight of the hydroxyalkyl (meth) acrylate is preferably 40 or more, more preferably 80 or more, and from the viewpoint of mechanical strength of the resulting cured film, it is 800 or less, and further 400 or less. preferable. In addition, when (3) hydroxyalkyl (meth) acrylate is the above addition reactant or polymer, the molecular weight is a number average molecular weight.

(4) Other raw material compounds The raw material compound for producing the urethane (meth) acrylate oligomer in the present invention may further contain other components as long as the effects of the present invention are obtained. Examples of such other components include a high molecular weight polyol having a number average molecular weight of 500 or more other than the specific polycarbonate diol, a low molecular weight polyol having a number average molecular weight of less than 500, and a chain extender.

  The high molecular weight polyol is a compound other than a specific polycarbonate diol having two or more hydroxyl groups having a number average molecular weight of 500 or more. Although there is no restriction | limiting in particular in the upper limit of the number average molecular weight of high molecular weight polyol, Usually, it is 10,000 or less. 1 type may be used for the said high molecular weight polyol, and 2 or more types may be used for it.

  Examples of such high molecular weight polyols include polyether diols, polyester diols, polyether ester diols, polycarbonate diols other than the specific polycarbonate diol, polyolefin polyols, and silicon polyols. From the viewpoint of improving water resistance and heat resistance, polycarbonate diol is preferred.

  Examples of the polyether diol include compounds obtained by ring-opening polymerization of cyclic ethers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. These may use 1 type and may use 2 or more types.

  Examples of the polyester diol include compounds obtained by polycondensation of a dicarboxylic acid or its anhydride and a low molecular weight diol, such as polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, and polybutylene sebacate. Is mentioned. These may use 1 type and may use 2 or more types. Examples of the polyester diol include compounds obtained by ring-opening polymerization of a lactone with a low molecular weight diol, such as polycaprolactone and polymethylvalerolactone. These may use 1 type and may use 2 or more types.

  Examples of the dicarboxylic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, isophthalic acid, and phthalic acid. Examples of these products include these anhydrides. Examples of the low molecular weight diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and polytetramethylene. Glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl- Examples include 1,3-pentanediol, 3,3-dimethylolheptane, 1,9-nonanediol, 2-methyl-1,8-octanediol, cyclohexanedimethanol, and bishydroxyethoxybenzene. .

  Examples of the polyether ester diol include a compound obtained by ring-opening polymerization of a cyclic ether to the polyester diol, and a compound obtained by polycondensation of the polyether diol and the dicarboxylic acid, such as poly (polytetramethylene ether) adipate. Is mentioned. These may use 1 type and may use 2 or more types.

  Examples of the other polycarbonate diol include polybutylene carbonate, polypentamethylene carbonate, polyhexamethylene carbonate, poly (2-methyl-) obtained by deglycolization or dealcoholization from the low molecular weight diol and alkylene carbonate or dialkyl carbonate. And propylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, polycyclohexylene carbonate, and the like, and copolymers thereof. These may use 1 type and may use 2 or more types.

  The polyolefin polyol is a polyolefin having two or more hydroxyl groups, and examples thereof include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol. These may use 1 type and may use 2 or more types.

  The silicon polyol is a silicone having two or more hydroxyl groups, and examples of the silicon polyol include polydimethylsiloxane polyol. These may use 1 type and may use 2 or more types.

  Among these, from the viewpoint of weather resistance and mechanical strength of a cured product obtained by curing the active energy ray-curable polymer composition, the high molecular weight polyol is preferably the other polycarbonate diol. .

  When the number average molecular weight of the other polycarbonate diol is not excessively large, the workability is good without significantly increasing the viscosity of the resulting urethane (meth) acrylate oligomer, and the active energy ray-curable polymer. There is a tendency that the mechanical strength and stain resistance of a cured product obtained by curing the composition are improved. From such a viewpoint, the number average molecular weight of the other polycarbonate diol is preferably 10,000 or less, more preferably 5,000 or less, and further preferably 2,000 or less.

  The low molecular weight polyol is a compound having two or more hydroxyl groups having a number average molecular weight of less than 500. 1 type may be used for a low molecular weight polyol, and 2 or more types may be used for it.

  Examples of such low molecular weight polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, and 2-methyl-1,3-propane. Diol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1 , 5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6 -Hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 3,3 Aliphatic diols such as dimethylol heptane, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol; cyclopropanediol, cyclopropanedimethanol, cyclopropanediethanol, cyclopropanedi Propanol, cyclopropanedibutanol, cyclopentanediol, cyclopentanedimethanol, cyclopentanediethanol, cyclopentanedipropanol, cyclopentanedibutanol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, cyclohexanedipropanol, cyclohexanedibutanol, cyclohexenediol , Cyclohexene dimethanol, cyclohexene diethanol, cyclohexene dipropanol, cyclohex Alicyclic diols such as dibutanol, cyclohexadiene diol, cyclohexadiene dimethanol, cyclohexadiene diethanol, cyclohexadiene dipropanol, cyclohexadiene dibutanol, hydrogenated bisphenol A, tricyclodecane diol, adamantyl diol; bishydroxyethoxybenzene, Aromatic diols such as bishydroxyethyl terephthalate and bisphenol-A; dialkanolamines such as N-methyldiethanolamine; pentaerythritol; sorbitol; mannitol; glycerin; and trimethylolpropane.

  Among these, from the viewpoint of the weather resistance of the obtained cured film, the low molecular weight polyol is preferably an aliphatic diol or an alicyclic diol. In particular, in applications where the mechanical strength of the cured product is required, the low molecular weight polyol is ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propane. An aliphatic diol having 1 to 4 carbon atoms between hydroxyl groups such as diol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol; 1,4-cyclohexanedimethanol, Particularly preferred is an alicyclic diol in which two hydroxyl groups such as hydrogenated bisphenol A are present at symmetrical positions with an alicyclic structure in between.

  The number average molecular weight of the low molecular weight polyol is preferably 50 or more from the viewpoint of the balance between elongation and elastic modulus as a cured product obtained by curing the active energy ray-curable polymer composition, 250 or less, more preferably 150 or less.

  The chain extender is a compound having two or more active hydrogens that react with an isocyanate group. One type of chain extender may be used, or two or more types may be used.

  Examples of such chain extenders include low molecular weight diamine compounds having a number average molecular weight of less than 500, such as 2,4- or 2,6-tolylenediamine, xylylenediamine, 4,4′-diphenylmethanediamine, and the like. Aromatic diamines: ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 2,2,4 -Or aliphatic such as 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, etc. Diamines; and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 4,4′-di And alicyclic diamines such as cyclohexylmethanediamine (hydrogenated MDA), isopropylidenecyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, and tricyclodecanediamine; It is done.

[Urethane (meth) acrylate oligomer]
Next, the urethane (meth) acrylate oligomer of the present invention obtained from the above raw material compound and the production method thereof will be described.

The urethane (meth) acrylate oligomer of the present invention is produced by subjecting the (1) polyisocyanate to the addition reaction of the specific polycarbonate diol (2) polycarbonate diol and the (3) hydroxyalkyl (meth) acrylate. be able to. When the high molecular weight polyol, the low molecular weight polyol, and the chain extender that are other raw material compounds are used in combination, the urethane (meth) acrylate oligomer of the present invention is further added to the (1) polyisocyanate. Other raw material compounds can also be produced by addition reaction.
In addition, the charging ratio of each raw material compound at that time is substantially equal to or the same as the composition of the target urethane (meth) acrylate oligomer.

  These addition reactions can be performed by any known method. Examples of such a method include the following methods (a) to (c).

(A) An isocyanate-terminated urethane prepolymer obtained by reacting a component other than the hydroxyalkyl (meth) acrylate with a polyisocyanate under conditions such that an isocyanate group is excessive is obtained, and then the isocyanate-terminated urethane prepolymer and the above-mentioned A prepolymer method in which a hydroxyalkyl (meth) acrylate is reacted.
(B) One-shot method in which all raw material compounds are added simultaneously and reacted.
(C) obtained by reacting the polyisocyanate with the hydroxyalkyl (meth) acrylate first, and synthesizing a urethane (meth) acrylate prepolymer having a (meth) acryloyl group and an isocyanate group in the molecule at the same time. A method of reacting raw material compounds other than these with a prepolymer.

  Among these, according to the method (a), the urethane prepolymer is obtained by urethanation reaction of the polyisocyanate and the polycarbonate diol, and the resulting urethane (meth) acrylate oligomer has an isocyanate group at the terminal. The method (a) is preferred from the viewpoint that the molecular weight can be controlled and an acryloyl group can be introduced at both ends because the urethane prepolymer has a structure obtained by urethanation with the hydroxyalkyl (meth) acrylate.

  The amount of all isocyanate groups in the urethane (meth) acrylate oligomer of the present invention and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually theoretically equimolar.

  That is, the amount of the (1) polyisocyanate, (2) polycarbonate diol, (3) hydroxyalkyl (meth) acrylate, and other raw material compounds used in producing the urethane (meth) acrylate oligomer of the present invention is In the urethane (meth) acrylate oligomer of the present invention, the amount of all isocyanate groups and the amount of all functional groups reacting therewith are 50 to 200 mol% in terms of equimolar or mol% of the all functional groups relative to the isocyanate group. Amount.

  When producing the urethane (meth) acrylate oligomer of the present invention, the amount of (3) hydroxyalkyl (meth) acrylate used is (3) hydroxyalkyl (meth) acrylate, (2) polycarbonate diol, and if necessary. The other high-molecular weight polyols, low-molecular-weight polyols, and chain extenders that are used as other raw material compounds are usually 10 mol% or more, preferably 15%, based on the total amount of compounds containing functional groups that react with isocyanates. More mol% or more, more preferably 25 mol% or more, and usually 70 mol% or less, preferably 50 mol% or less. According to this ratio, the molecular weight of the urethane (meth) acrylate oligomer obtained can be controlled. When the proportion of hydroxyalkyl (meth) acrylate is large, the molecular weight of the urethane (meth) acrylate oligomer tends to be small, and when the proportion is small, the molecular weight tends to be large.

The use amount of the specific polycarbonate diol is preferably 25 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol% with respect to the total use amount of the specific polycarbonate diol and the high molecular weight polyol. That's it. When the usage-amount of the said specific polycarbonate diol is larger than the said lower limit, there exists a tendency for the hardness and stain resistance of the hardened | cured material obtained to become favorable, and it is preferable.
Further, the amount of the specific polycarbonate diol used is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably based on the total amount of the specific polycarbonate diol and the high molecular weight polyol used. It is 50 mass% or more, Most preferably, it is 70 mass% or more. When the amount of the specific polycarbonate diol used is larger than the lower limit, the viscosity of the resulting composition is lowered and workability is improved, and the mechanical strength, hardness and wear resistance of the resulting cured product are improved. This is preferable.

  Furthermore, the use amount of the specific polycarbonate diol is preferably 25 mol% or more, more preferably 50 mol%, based on the total use amount of the specific polycarbonate diol, the high molecular weight polyol and the low molecular weight polyol. As mentioned above, More preferably, it is 70 mol% or more. When the amount of the specific polycarbonate diol used is larger than the lower limit, it is preferable because the elongation and weather resistance of the obtained cured product tend to be improved.

  Further, when a chain extender is used, the amount of the total polyol used relative to the total amount of the specific polycarbonate diol, the high molecular weight polyol, and the compound of all the low molecular weight polyols combined with the chain extender. Is preferably at least 70 mol%, more preferably at least 80 mol%, even more preferably at least 90 mol%, particularly preferably at least 95 mol%. When the total amount of polyol is larger than the lower limit, the liquid stability tends to be improved, which is preferable.

  In the production of the urethane (meth) acrylate oligomer of the present invention, a solvent can be used for the purpose of adjusting the viscosity. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types. As the solvent, any known solvent can be used as long as the effects of the present invention are obtained. Preferable solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. The solvent can usually be used in an amount of less than 300 parts by mass with respect to 100 parts by mass of the solid content in the reaction system.

  In the production of the urethane (meth) acrylate oligomer of the present invention, the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compound is preferably 20% by mass or more based on the total amount of the reaction system. 40% by mass or more is more preferable. In addition, the upper limit of this total content is 100 mass%. It is preferable for the total content of the urethane (meth) acrylate oligomer and its raw material compound to be 20% by mass or more because the reaction rate tends to increase and the production efficiency tends to improve.

An addition reaction catalyst can be used in the production of the urethane (meth) acrylate oligomer of the present invention. The addition reaction catalyst can be selected from the range in which the effects of the present invention can be obtained, and examples thereof include dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, and dioctyltin dioctoate. An addition reaction catalyst may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, the addition reaction catalyst is preferably dioctyltin dilaurate from the viewpoints of environmental adaptability, catalytic activity, and storage stability.
The addition reaction catalyst has an upper limit of usually 1000 ppm or less, preferably 500 ppm or less, and a lower limit of usually 10 ppm or more, preferably 30 ppm or more, with respect to the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compounds. Used.

Moreover, when the (meth) acryloyl group is included in the reaction system during the production of the urethane (meth) acrylate oligomer of the present invention, a polymerization inhibitor can be used in combination. Such a polymerization inhibitor can be selected from the range in which the effects of the present invention can be obtained, for example, phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, dibutylhydroxytoluene, amines such as phenothiazine and diphenylamine, Examples thereof include copper salts such as copper dibutyldithiocarbamate, manganese salts such as manganese acetate, nitro compounds, and nitroso compounds. A polymerization inhibitor may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, phenols are preferable as the polymerization inhibitor.
The polymerization inhibitor has an upper limit of usually 3000 ppm or less, preferably 1000 ppm or less, particularly preferably 500 ppm or less, and a lower limit usually based on the total content of the urethane (meth) acrylate oligomer and raw material compounds to be produced. It is used at 50 ppm or more, preferably 100 ppm or more.

  In the production of the urethane (meth) acrylate oligomer of the present invention, the reaction temperature is usually 20 ° C. or higher, preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. A reaction temperature of 20 ° C. or higher is preferable because the reaction rate increases and the production efficiency tends to improve. Moreover, reaction temperature is 120 degrees C or less normally, and it is preferable that it is 100 degrees C or less. It is preferable for the reaction temperature to be 120 ° C. or lower because side reactions such as an allohanato reaction hardly occur. When the reaction system contains a solvent, the reaction temperature is preferably lower than the boiling point of the solvent. When (meth) acrylate is contained, the reaction temperature is 70 ° C. from the viewpoint of preventing the reaction of the (meth) acryloyl group. The following is preferable. The reaction time is usually about 5 to 20 hours.

  The number average molecular weight of the urethane (meth) acrylate oligomer thus obtained is preferably 500 or more, particularly 1000 or more, preferably 10,000 or less, particularly 5000 or less, and particularly preferably 3000 or less. When the number average molecular weight of the urethane (meth) acrylate oligomer is not less than the above lower limit, the resulting cured film has good three-dimensional workability and tends to have an excellent balance between three-dimensional workability and stain resistance. When the number average molecular weight of the urethane (meth) acrylate oligomer is not more than the above upper limit, the cured film obtained from the composition has good contamination resistance and tends to have a good balance between three-dimensional processability and contamination resistance. Therefore, it is preferable. This is because the three-dimensional workability and stain resistance depend on the distance between the cross-linking points in the network structure, and as this distance increases, the structure becomes flexible and easily stretched, and the three-dimensional workability is superior. This is presumed to be because the structure becomes a strong structure and is excellent in stain resistance.

[Active energy ray-curable polymer composition]
Below, the active energy ray-curable polymer composition of this invention containing the above-mentioned urethane (meth) acrylate type oligomer is demonstrated.

  The active energy ray-curable polymer composition of the present invention preferably has a molecular weight between calculated network crosslinking points of 500 to 10,000.

  In the present specification, the molecular weight between calculated network cross-linking points of the composition is the average molecular weight between active energy ray reactive groups (hereinafter sometimes referred to as “cross-linking points”) that form a network structure in the entire composition. Represents a value. The molecular weight between the calculated network crosslinking points correlates with the network area at the time of forming the network structure, and the larger the calculated molecular weight between the crosslinking points, the lower the crosslinking density. In the reaction by active energy ray curing, when a compound having only one active energy ray reactive group (hereinafter, sometimes referred to as “monofunctional compound”) reacts, it becomes a linear polymer, while the active energy A network structure is formed when a compound having two or more linear reactive groups (hereinafter sometimes referred to as “polyfunctional compound”) reacts.

  Therefore, the active energy ray reactive group of the polyfunctional compound is a crosslinking point, and the calculation of the molecular weight between the calculated network crosslinking points is centered on the polyfunctional compound having the crosslinking point, and the monofunctional compound has the polyfunctional compound. The molecular weight between the crosslinking points is treated as having an effect of extending the molecular weight, and the molecular weight between the calculation network crosslinking points is calculated. In addition, the calculation of the molecular weight between the calculation network crosslinking points is performed on the assumption that all the active energy ray reactive groups have the same reactivity and that all the active energy ray reactive groups react by irradiation with the active energy ray. .

  In a polyfunctional compound single-system composition in which only one type of polyfunctional compound reacts, the molecular weight between the calculated network cross-linking points is twice the average molecular weight per active energy ray reactive group of the polyfunctional compound. . For example, (1000/2) × 2 = 1000 for a bifunctional compound with a molecular weight of 1,000, and (300/3) × 2 = 200 for a trifunctional compound with a molecular weight of 300.

  In a polyfunctional compound mixed system composition in which multiple types of polyfunctional compounds react, the average value of the molecular weights between the calculated network cross-linking points of each of the above single systems with respect to the total number of active energy ray reactive groups contained in the composition is This is the molecular weight between the calculated network crosslinking points of the composition. For example, in a composition comprising a mixture of 4 moles of a bifunctional compound having a molecular weight of 1,000 and 4 moles of a trifunctional compound having a molecular weight of 300, the total number of reactive energy ray reactive groups in the composition is 2 × 4 + 3 × 4 = 20. The molecular weight between the calculated network cross-linking points of the composition is {(1000/2) × 8 + (300/3) × 12} × 2/20 = 520.

  When a monofunctional compound is included in the composition, a molecule formed by calculation and equimolar to the active energy ray reactive group (that is, the crosslinking point) of the polyfunctional compound, and the monofunctional compound linked to the crosslinking point Assuming that the reaction takes place in the middle of the chain, the extension of the molecular chain by the monofunctional compound at one crosslinking point is the total molecular weight of the monofunctional compound, and the total active energy ray reaction of the polyfunctional compound in the composition. Half of the value divided by the radix. Here, since the molecular weight between the calculated network cross-linking points is considered to be twice the average molecular weight per cross-linking point, the amount extended by the monofunctional compound relative to the calculated molecular weight between the cross-linking points calculated for the polyfunctional compound is The value obtained by dividing the total molecular weight of the monofunctional compound by the total number of reactive energy ray reactive groups of the polyfunctional compound in the composition.

  For example, in a composition comprising a mixture of 40 mol of a monofunctional compound having a molecular weight of 100 and 4 mol of a bifunctional compound having a molecular weight of 1,000, the number of reactive energy ray reactive groups of the polyfunctional compound is 2 × 4 = 8. The extension due to the monofunctional compound in the molecular weight between the calculated network cross-linking points is 100 × 40/8 = 500. That is, the molecular weight between calculated network crosslinks of the composition is 1000 + 500 = 1500.

From the above, in the mixture of monofunctional compounds M _A molar molecular weight W _A, and f _B functional compound M _B mol molecular weight W _B, and f _C functional compound M _C mol molecular weight W _C, the composition The molecular weight between the calculated network cross-linking points of the product can be expressed by the following formula.

  The molecular weight between the calculated network crosslinking points of the active energy ray-curable polymer composition of the present invention calculated in this way is preferably 500 or more, more preferably 800 or more, and 1,000 or more. More preferably, it is preferably 10,000 or less, more preferably 8,000 or less, further preferably 6,000 or less, and even more preferably 4,000 or less. 3,000 or less is particularly preferable.

  A molecular weight between calculated network crosslinking points of 10,000 or less is preferable because the cured film obtained from the composition has good stain resistance and tends to have a good balance between three-dimensional processability and stain resistance. Moreover, it is preferable that the molecular weight between the calculation network cross-linking points is 500 or more because the obtained cured film has good three-dimensional workability and tends to have an excellent balance between the three-dimensional workability and the stain resistance. This is because the three-dimensional workability and stain resistance depend on the distance between the cross-linking points in the network structure. When this distance is increased, the structure becomes flexible and easily stretched, and the three-dimensional processability is excellent. This is presumed to be because the structure becomes a strong structure and is excellent in stain resistance.

  The active energy ray-curable polymer composition of the present invention may further contain other components other than the urethane (meth) acrylate oligomer of the present invention as long as the effects of the present invention are obtained. Examples of such other components include an active energy ray reactive monomer, an active energy ray curable oligomer, a polymerization initiator, a photosensitizer, an additive, and a solvent.

  In the active energy ray-curable polymer composition of the present invention, the content of the urethane (meth) acrylate oligomer of the present invention is equal to the total amount of active energy ray reactive components including the urethane (meth) acrylate oligomer of the present invention. It is preferable that it is 40 mass% or more with respect to it, and it is more preferable that it is 60 mass% or more. In addition, the upper limit of this content is 100 mass%. When the content of the urethane (meth) acrylate oligomer is 40% by mass or more, the curability is good and the three-dimensional workability tends to be improved without excessively increasing the mechanical strength of the cured product. This is preferable.

  In the active energy ray-curable polymer composition of the present invention, the content of the urethane (meth) acrylate oligomer of the present invention is preferably large in terms of elongation and film-forming property, and on the other hand, The smaller one is preferable in terms of viscosity. From such a viewpoint, the content of the urethane (meth) acrylate oligomer of the present invention is 50% by mass or more based on the total amount of all components including other components in addition to the active energy ray reactive component. It is preferably 70% by mass or more. In addition, the upper limit of content of the urethane (meth) acrylate oligomer of this invention is 100 mass%, and it is preferable that this content is less than that.

  Further, in the active energy ray-curable polymer composition of the present invention, the total content of the active energy ray-reactive component containing the urethane (meth) acrylate oligomer of the present invention is determined by the curing rate and surface of the composition. From the standpoint of excellent curability and no tack remaining, it is preferably 60% by mass or more, more preferably 80% by mass or more, and 90% by mass or more based on the total amount of the composition. Is more preferable, and it is still more preferable that it is 95 mass% or more. In addition, the upper limit of this content is 100 mass%.

  Any known active energy ray-reactive monomer can be used as the active energy ray-reactive monomer as long as the effects of the present invention are obtained. These active energy ray-reactive monomers are intended to adjust the hydrophilicity / hydrophobicity of the urethane (meth) acrylate oligomer of the present invention and the physical properties such as hardness and elongation of the cured product when the resulting composition is a cured product. Used in etc. An active energy ray reactive monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Examples of such active energy ray reactive monomers include vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specific examples include styrene, α-methylstyrene, α-chlorostyrene. Aromatic vinyl monomers such as vinyltoluene and divinylbenzene; vinyl such as vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate Ester monomers; Vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; Allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether, and allyl glycidyl ether; (meth) acrylamide, N, N-dimethylacrylamide N, N-dimethylmethacrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (meth) acryloylmorpholine (Meth) acrylamides such as methylenebis (meth) acrylamide; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate-n-butyl , (Meth) acrylic acid-i-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid Stearyl, tetrahydrofurfuryl (meth) acrylate, (meth) a Morpholyl laurate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate , (Meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid allyl, (meth) acrylic acid-2-ethoxyethyl, (meth) acrylic acid isobornyl, (meth) Monofunctional (meth) acrylic acid such as phenyl acrylate And ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate ( n = 5-14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, di (meth) Polypropylene glycol acrylate (n = 5-14), di (meth) acrylic acid-1,3-butylene glycol, di (meth) acrylic acid-1,4-butanediol, di (meth) acrylic acid polybutylene glycol ( n = 3-16), di (meth) acrylic acid poly Li (1-methylbutylene glycol) (n = 5-20), di (meth) acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonanediol, di (meth) acrylic acid Neopentyl glycol, hydroxypivalate neopentyl glycol di (meth) acrylate, di (meth) acrylate dicyclopentanediol, di (meth) acrylate tricyclodecane, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hex (Meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpropane polyoxypropyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate , Propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, tri Black decanedimethanol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, polyfunctional (meth) acrylates such as bisphenol F epoxy di (meth) acrylate; and the like.

  Among these, in particular, in applications where coating properties are required for the composition of the present invention, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate , Molecules such as trimethylcyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, etc. A monofunctional (meth) acrylate having a ring structure in the inside thereof is preferable. On the other hand, in applications where mechanical strength of the resulting cured product is required, di (meth) acrylic acid-1,4-butanediol, di (meth) ) Acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonane Dipentaglycol di (meth) acrylate, tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Polyfunctional (meth) acrylates such as erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are preferred.

  In the active energy ray-curable polymer composition of the present invention, the content of the active energy ray-reactive monomer is selected from the viewpoints of adjusting the viscosity of the composition and adjusting physical properties such as hardness and elongation of the resulting cured product. It is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and still more preferably 10% by mass or less, based on the total amount of the composition. .

  The active energy ray-curable oligomer may be used alone or in combination of two or more. Examples of the active energy ray-curable oligomer include epoxy (meth) acrylate oligomers and acrylic (meth) acrylate oligomers.

  In the active energy ray-curable polymer composition of the present invention, the content of the active energy ray-reactive oligomer is based on the total amount of the composition from the viewpoint of adjusting physical properties such as hardness and elongation of the obtained cured product. 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and further more preferably 10% by mass or less.

  The polymerization initiator is mainly used for the purpose of improving the initiation efficiency of a polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams. As the polymerization initiator, a photoradical polymerization initiator which is a compound having a property of generating radicals by light is generally used, and any known photoradical polymerization initiator can be used as long as the effects of the present invention can be obtained. It is. A polymerization initiator may be used individually by 1 type, and 2 or more types may be mixed and used for it. Furthermore, you may use together radical photopolymerization initiator and a photosensitizer.

  Examples of the photo radical polymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methyl orthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chloro Thioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoylformate, 2-methyl-1- [4- ( Tilthio) phenyl] -2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl]- Phenyl] -2-methyl-propan-1-one and the like.

  Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6, since the curing speed is high and the crosslinking density can be sufficiently increased. -Trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ] 2-Methyl-propan-1-one is more preferred.

  In addition, when the active energy ray-curable polymer composition contains a compound having a cationic polymerizable group such as an epoxy group together with a radical polymerizable group, as a polymerization initiator, a photocation together with the above-mentioned photo radical polymerization initiator. A polymerization initiator may be included. Any known cationic photopolymerization initiator can be used as long as the effects of the present invention can be obtained.

  The content of these polymerization initiators in the active energy ray-curable polymer composition of the present invention is preferably 10 parts by mass or less with respect to a total of 100 parts by mass of the active energy ray reactive components, More preferably, it is 5 parts by mass or less. It is preferable for the content of the photopolymerization initiator to be 10 parts by mass or less because the mechanical strength is not easily lowered by the initiator decomposition product.

  The photosensitizer can be used for the same purpose as the polymerization initiator. A photosensitizer may be used individually by 1 type and may be used in mixture of 2 or more types. As the photosensitizer, any known photosensitizer can be used as long as the effects of the present invention are obtained. Examples of such photosensitizers include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, And 4-dimethylaminoacetophenone.

  In the active energy ray-curable polymer composition of the present invention, the content of the photosensitizer is preferably 10 parts by mass or less with respect to 100 parts by mass in total of the active energy ray reactive components. More preferably, it is 5 parts by mass or less. It is preferable for the content of the photosensitizer to be 10 parts by mass or less, since it is difficult for mechanical strength to decrease due to a decrease in crosslink density.

  The additive is optional as long as the effects of the present invention are obtained, and various materials added to a composition used for the same application can be used as the additive. An additive may be used individually by 1 type, and 2 or more types may be mixed and used for it. Examples of such additives include glass fiber, glass bead, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc, kaolin, metal oxide, metal fiber, iron, lead, and metal powder. Fillers such as carbon fibers, carbon black, graphite, carbon nanotubes, carbon materials such as fullerenes such as C60 (fillers and carbon materials may be collectively referred to as “inorganic components”); Agent, heat stabilizer, UV absorber, HALS (hindered amine light stabilizer), anti-fingerprint agent, surface hydrophilizing agent, antistatic agent, slipperiness imparting agent, plasticizer, mold release agent, antifoaming agent, leveling agent, Anti-settling agents, surfactants, thixotropy imparting agents, lubricants, flame retardants, flame retardant aids, polymerization inhibitors, fillers, silane coupling agents and other modifiers; pigments, dyes, hue adjustments Colorants and the like; and, monomer and / or oligomer thereof, or a curing agent required for the synthesis of inorganic components, catalysts, curing accelerators like; and the like.

  In the active energy ray-curable polymer composition of the present invention, the content of the additive is preferably 10 parts by mass or less with respect to 100 parts by mass in total of the active energy ray reactive components. It is more preferable that the amount is not more than part by mass. It is preferable for the content of the additive to be 10 parts by mass or less because it is difficult for the mechanical strength to decrease due to a decrease in crosslinking density.

  The solvent is used for the purpose of adjusting the viscosity of the active energy ray-curable polymer composition of the present invention, for example, depending on the coating method for forming the coating film of the active energy ray-curable polymer composition of the present invention. Can be used. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types. As the solvent, any known solvent can be used as long as the effects of the present invention are obtained. Preferable solvents include toluene, xylene, ethyl acetate, butyl acetate, isopropanol, isobutanol, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. A solvent can be normally used in less than 200 mass parts with respect to 100 mass parts of solid content of an active energy ray curable polymer composition.

  There are no particular limitations on the method of incorporating the active energy ray-curable polymer composition of the present invention into optional components such as the aforementioned additives, and examples thereof include conventionally known mixing and dispersion methods. In addition, in order to disperse | distribute the said arbitrary component more reliably, it is preferable to perform a dispersion | distribution process using a disperser. Specifically, for example, two rolls, three rolls, bead mill, ball mill, sand mill, pebble mill, tron mill, sand grinder, seg barrier striker, planetary stirrer, high speed impeller disperser, high speed stone mill, high speed impact mill , A kneader, a homogenizer, an ultrasonic disperser and the like.

  The viscosity of the active energy ray-curable polymer composition of the present invention can be appropriately adjusted according to the use and usage of the composition, but the viewpoints of handleability, coatability, moldability, three-dimensional formability, etc. From the above, the viscosity at 25 ° C. in an E-type viscometer (rotor 1 ° 34 ′ × R24) is preferably 10 mPa · s or more, more preferably 100 mPa · s or more, 000 mPa · s or less is preferable, and 50,000 mPa · s or less is more preferable. The viscosity of the active energy ray-curable polymer composition can be adjusted by, for example, the content of the urethane (meth) acrylate oligomer of the present invention, the type of the optional component, the blending ratio thereof, and the like.

  As a coating method of the active energy ray-curable polymer composition of the present invention, a bar coater method, an applicator method, a curtain flow coater method, a roll coater method, a spray method, a gravure coater method, a comma coater method, a reverse roll coater method Known methods such as a lip coater method, a die coater method, a slot die coater method, an air knife coater method and a dip coater method can be applied. Among them, a bar coater method and a gravure coater method are preferable.

[Curing film and laminate]
The active energy ray-curable polymer composition of the present invention can be made into a cured film by irradiating this with active energy rays.

  As the active energy rays used when the composition is cured, infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. It is preferable to use an electron beam or an ultraviolet ray from the viewpoint of apparatus cost and productivity. As a light source, an electron beam irradiation apparatus, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Ar Lasers, He—Cd lasers, solid lasers, xenon lamps, high frequency induction mercury lamps, sunlight, and the like are suitable.

The irradiation amount of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, when curing is performed by electron beam irradiation, the irradiation amount is preferably 1 to 10 Mrad. Moreover, in the case of ultraviolet irradiation, it is preferable that it is 50-1,000 mJ / cm < ² >. The atmosphere during curing may be air, an inert gas such as nitrogen or argon. Moreover, you may irradiate in the sealed space between a film or glass, and a metal metal mold | die.

  The thickness of the cured film of the present invention is appropriately determined according to the intended use, but the lower limit is preferably 1 μm, more preferably 3 μm, and particularly preferably 5 μm. The upper limit is preferably 200 μm, more preferably 100 μm, particularly preferably 50 μm. When the film thickness is 1 μm or more, the design properties and functionality after three-dimensional processing are improved, and when it is 200 μm or less, the internal curability and the three-dimensional workability are preferable. In industrial use, the lower limit is preferably 1 μm, and the upper limit is preferably 100 μm, more preferably 50 μm, particularly preferably 20 μm, and most preferably 10 μm.

According to this invention, the laminated body which has a layer which consists of said cured film of this invention on a base material can be obtained.
The laminate of the present invention is not particularly limited as long as it has a layer comprising the cured film of the present invention, and a layer other than the substrate and the cured film of the present invention is interposed between the substrate and the cured film of the present invention. You may have, and you may have on the outer side. Moreover, the said laminated body may have multiple layers of the base material and the cured film of this invention.

  As a method for obtaining the laminate of the present invention having a multi-layered cured film, all layers are laminated in an uncured state and then cured with active energy rays, the lower layer is cured with active energy rays, or semi-cured A method in which the upper layer is applied and then cured with active energy rays, a method in which each layer is applied to a release film or a base film, and then the layers are bonded together in an uncured or semi-cured state. Although a method is applicable, the method of hardening with an active energy ray after laminating | stacking in an uncured state from a viewpoint of improving the adhesiveness of an interlayer is preferable. As a method of laminating in an uncured state, a known method such as sequential coating in which the upper layer is applied after the lower layer is applied or simultaneous multilayer coating in which two or more layers are simultaneously applied from multiple slits is applied. Yes, but not necessarily.

  Examples of the base material include various shapes such as polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polypropylene and polyethylene, various plastics such as nylon, polycarbonate, and (meth) acrylic resin, or plates formed of metal. The article is mentioned.

  The cured film of the present invention can be a film having excellent stain resistance and hardness against general household contaminants such as ink and ethanol, and the present invention using the cured film of the present invention as a coating on various substrates. The laminate can be excellent in design and surface protection.

In addition, the active energy ray-curable polymer composition of the present invention is capable of following deformation during three-dimensional processing, taking into account the molecular weight between the calculation network cross-linking points, elongation at break, mechanical strength, contamination resistance. A cured film having both properties and hardness can be provided.
Moreover, it is expected that the active energy ray-curable polymer composition of the present invention can easily produce a thin film-like resin sheet by single-layer coating.

  The breaking elongation of the cured film of the present invention was determined by cutting the cured film of the present invention into a width of 10 mm and using a Tensilon tensile tester (Orientec, Tensilon UTM-III-100) at a temperature of 23 ° C. and a tensile rate. The value measured by performing a tensile test under the conditions of 50 mm / min and a distance between chucks of 50 mm is preferably 50% or more, more preferably 75% or more, and further preferably 100% or more, It is particularly preferably 120% or more.

  The cured film of the present invention and the laminate of the present invention can be used as a coating substitute film, and can be effectively applied to, for example, interior and exterior building materials, automobiles, home appliances, and other various members. is there.

  Specific examples of the present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited by these examples unless it exceeds the gist.

[Measurement and evaluation methods for various physical properties and characteristic values]
<Calculation method of number average molecular weight of urethane (meth) acrylate oligomer>
The urethane (meth) acrylate oligomers of the examples and comparative examples contain three types of components, polyisocyanate, polycarbonate diol, and hydroxyalkyl (meth) acrylate, as constituent units. Since these structural units are formed while maintaining the molecular weight of each component in the urethane (meth) acrylate oligomer, in this example and the comparative example, until the urethane (meth) acrylate oligomer is generated. The number average molecular weight (calculated value) of the urethane (meth) acrylate oligomer was calculated by the sum of the products of the molar ratio of each component and the molecular weight of each component.

<Measurement of number average molecular weight of urethane (meth) acrylate oligomer by GPC>
Using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation), THF as a solvent, polystyrene as a standard sample, TSKgel superH1000 + H2000 + H3000 as a column, a liquid feed rate of 0.5 mL / min, a column oven temperature of 40 ° C., urethane ( The number average molecular weight (GPC measurement value) of the (meth) acrylate oligomer was measured.

<Calculation of molecular weight between calculation network cross-linking points of urethane (meth) acrylate oligomer>
The molecular weight between the calculated network cross-linking points of the urethane (meth) acrylate oligomer in each example and comparative example is that the reactive groups for the hydroxyalkyl (meth) acrylate in the prepolymer of the urethane acrylate oligomer are isocyanate groups at both ends of the prepolymer. Yes, since the hydroxyalkyl (meth) acrylate bonded with urethane bonds to both ends of the prepolymer is added by radical polymerization, the crosslinking point of the urethane acrylate oligomer in the composition is both the urethane (meth) acrylate oligomer Since it becomes a (meth) acryloyl group located at the terminal, and therefore in the following Examples and Comparative Examples, the active energy ray-curable polymer composition becomes a bifunctional (polyfunctional) compound single-system composition described above, It calculated | required from the following formula.

<Mechanical properties of cured film>
The cured film was cut to a width of 10 mm, and using a Tensilon tensile tester (Orientec, Tensilon UTM-III-100), the temperature was 23 ° C., the relative humidity was 53%, the tensile speed was 50 mm / min, and the distance between chucks was 50 mm. Tensile tests were performed under the conditions, and stress at the time of 1%, 5%, 10%, 50%, and 100% tension (hereinafter referred to as “M1”, “M5”, “M10”, “M50”, and “M100”, respectively). The breaking elongation and breaking strength were measured.

<Pencil hardness of cured film>
Using a wear tester (manufactured by Shinto Kagaku; Haydon Dynamic strain amplifier 3K-34B) and having a hardness of 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H (Mitsubishi Pencil Co., Ltd .; (Product No. UNI, Nikko-inspected, for pencil scratch value test) were evaluated under the conditions of 23 ° C./53% RH. A pencil having a hardness of 6B was attached to the wear tester, and it was run for 1 cm at a load of 1 kgf (9.8 N) and a scratching speed of 25 mm / min. When no running trace was observed, the pencil was replaced with a one-step hard pencil, and the same operation was repeated. The hardest pencil hardness at which no running trace was observed was taken as the evaluation result.

<Abrasion resistance of cured film (ΔH)>
Using a Gakushin Abrasion Tester (manufactured by Toyo Seiki), reciprocate 2000 times with a dry cloth (cotton-dye fastness test compliant with JIS L 0803) on the cured film, Haze difference of cured film before and after the test by Murakami Color Research Laboratory): ΔH was used as an evaluation result of wear resistance. The larger the ΔH value, the higher the haze of the cured film, and the lower the wear resistance.

[Synthesis Example 1: Synthesis of polycarbonate diol]
In a 1 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, 1,6-hexanediol: 195.0 g, neopentyl glycol: 207.4 g, diphenyl carbonate: 715.0 g, and magnesium acetate Tetrahydrate: 4.6 mg was added and replaced with nitrogen gas, and then the temperature was raised to an internal temperature of 160 ° C., and the contents were dissolved by heating and reacted for 60 minutes. Thereafter, the reaction was carried out while distilling off phenol and unreacted diol while lowering the pressure to 2 torr over 2 hours. Next, the reaction was carried out at 160 ° C. and 2 torr for 60 minutes to increase the polymerization degree of the polycarbonate diol. Further, nitrogen gas was bubbled for 12 hours while maintaining the pressure at 15 ° C. at 130 ° C., and the reaction was continued while removing phenol.
The yield of the obtained polycarbonate diol product was 452.6 g. The number average molecular weight determined from the hydroxyl value (58.49 mg-KOH / g) of the polycarbonate diol contained in the polycarbonate diol product is 2100, the molecular weight distribution (Mw / Mn) is 2.0, and 1,6-hexanediol. / Neopentyl glycol copolymer composition ratio (molar ratio) is 50/50 (1,6-HD / NPG = 50/50), polycarbonate diol-terminated 1,6-hexanediol / neopentyl glycol composition ratio (molar ratio) ) Was 32/68, and the terminal (A) ratio calculated by the formula (a) was 1.36. Moreover, the metal content of the residual catalyst in the obtained polycarbonate diol was 1.2 ppm.

The resulting polycarbonate diol-containing reaction product was a viscous liquid at room temperature, and fluidity was observed. The APHA value measured by comparison with a standard solution placed in a colorimetric tube was 30, and the viscosity measured by an E-type viscometer was 59 Pa · s at 40 ° C. Further, when impurities contained in the polycarbonate diol-containing reaction product were quantified by ¹ H-NMR, 1,6-hexanediol and neopentyl glycol, which are raw material diol compounds, were combined in 0.9 mass%, and cyclic carbonate. Although 2.5% by mass of neopentyl carbonate was contained, a phenoxy-terminated polymer, a polymer containing an ether bond, and phenol were not detected.

[Example 1]
A four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 110 g of isophorone diisocyanate as a polyisocyanate and 519 g of the polycarbonate diol obtained in Synthesis Example 1 as a polycarbonate diol, and further methyl ethyl ketone. 270 g was added and reacted for 9 hours while heating to 80 ° C. in an oil bath. After completion of the reaction, the mixture was cooled to 60 ° C., 0.21 g of dioctyltin dilaurate, 0.35 g of methylhydroquinone and 27 g of methyl ethyl ketone were added, and 63 g of 2-hydroxyethyl acrylate was added dropwise as a hydroxyalkyl (meth) acrylate to initiate the reaction. . The reaction is carried out for 10 hours while heating to 70 ° C. in an oil bath, the progress of the reaction is confirmed by a decrease in the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, and the end point of the reaction is confirmed by disappearance The urethane (meth) acrylate oligomer 1 was obtained. The solution of the urethane (meth) acrylate oligomer 1 thus obtained is referred to as an active energy ray-curable polymer composition 1.

  The composition ratio of the raw material compounds used for the production of this urethane (meth) acrylate oligomer 1 is polycarbonate diol / isophorone diisocyanate / 2-hydroxyethyl acrylate = 1/2 / 2.2 (molar ratio), The content of the resin component (solid content) is 70% by mass. The same conditions were used in Comparative Examples 1 and 2 below.

  The obtained active energy ray-curable polymer composition 1 had a molecular weight between calculated network crosslinking points of 2,780. The number average molecular weight of the urethane (meth) acrylate oligomer 1 determined by GPC was 2,670. Further, the content of the urethane (meth) acrylate oligomer 1 in the active energy ray-curable polymer composition 1 is 70% by mass, and the viscosity of the active energy ray-curable polymer composition 1 (E-type viscometer (rotor 1) The viscosity at 25 ° C. at 34 ° × R24) was 960 mPa · s.

Next, the obtained active energy ray-curable polymer composition 1 was coated on a polyethylene terephthalate film with an applicator to form a coating film, and then dried at 60 ° C. for 1 minute, and an electron beam irradiation apparatus (CB175, Eye The cured film 1 was formed by irradiating the dried coating film with an electron beam under the conditions of an acceleration voltage of 165 kV and an irradiation dose of 5 Mrad. Thereafter, the cured film 1 was peeled from the polyethylene terephthalate film to obtain a cured film 1 having a thickness of 50 μm.
About the obtained cured film 1, mechanical characteristics, abrasion resistance, and pencil hardness were evaluated. The results are shown in Table 1.

[Comparative Example 1]
As the polycarbonate diol, 110 g of isophorone diisocyanate was used as a commercially available polycarbonate diol ("Duranol T5652" manufactured by Asahi Kasei Corporation, number average molecular weight 2000, copolymer composition ratio of 1,6-hexanediol / 1,5-pentanediol (molar ratio). ) 50/50, hydroxyl value 56.1 mg-KOH / g) was used, 523 g of methyl ethyl ketone added before the prepolymer formation reaction was changed to 274 g, 27 g of methyl ethyl ketone added after completion of the prepolymer formation reaction was changed to 29 g, and 2-hydroxy Except for changing 63 g of ethyl acrylate to 67 g, the urethane (meth) acrylate oligomer 2 was obtained in the same manner as in Example 1, and the active energy ray which is also a solution of the urethane (meth) acrylate oligomer 2 To obtain a reduction polymer composition 2.

  The obtained active energy ray-curable polymer composition 2 had a molecular weight between calculated network crosslinking points of 2,680. Moreover, the number average molecular weight of the urethane (meth) acrylate oligomer 2 determined by GPC was 2,870. Furthermore, the content of the urethane (meth) acrylate oligomer 2 in the active energy ray-curable polymer composition 2 was 70% by mass, and the viscosity of the active energy ray-curable polymer composition 2 was 1390 mPa · s.

  Next, a cured film 2 was obtained in the same manner as in Example 1 except that the active energy ray-curable polymer composition 2 obtained as described above was used. About the obtained cured film 2, mechanical characteristics, abrasion resistance, and pencil hardness were evaluated. The results are shown in Table 1.

[Comparative Example 2]
As the polycarbonate diol, 110 g of isophorone diisocyanate was used, and 525 g of a commercially available polycarbonate diol (“Nipporan 980N” manufactured by Nippon Polyurethane Co., Ltd., number average molecular weight 2026, 1,6-hexanediol alone, hydroxyl value 55.4 mg-KOH / g) Urethane was used in the same manner as in Example 1 except that 270 g of methyl ethyl ketone added before the prepolymer formation reaction was changed to 274 g, 27 g of methyl ethyl ketone added after completion of the prepolymer formation reaction was changed to 28 g, and 63 g of hydroxyethyl acrylate was changed to 66 g. A (meth) acrylate oligomer 3 was obtained, and similarly, an active energy ray-curable polymer composition 3 which was a solution of the urethane (meth) acrylate oligomer 3 was obtained.

  The obtained active energy ray-curable polymer composition 3 had a molecular weight between calculated network crosslinking points of 2,710. The number average molecular weight of urethane (meth) acrylate oligomer 3 determined by GPC was 2,820. Furthermore, the content of the urethane (meth) acrylate oligomer 3 in the active energy ray-curable polymer composition 3 was 70% by mass, and the viscosity of the active energy ray-curable polymer composition 3 was 1560 mPa · s.

  Next, a cured film 3 was obtained in the same manner as in Example 1 except that the active energy ray-curable polymer composition 3 obtained as described above was used. About the obtained cured film 3, mechanical characteristics, abrasion resistance, and pencil hardness were evaluated. The results are shown in Table 1.

The following can be understood from the above results.
The polycarbonate polyol used in Example 1, Comparative Example 1 and Comparative Example 2, the urethane (meth) acrylate oligomer obtained and the active energy ray-curable polymer composition are all equivalent number average molecular weights, calculated crosslinks. Although it has an interstitial molecular weight and a hydroxyl value, 50% by mass of the structural unit of polycarbonate diol is 1,6-hexanediol, but in Example 1, the remaining 50% by mass of the structural unit is neopentyl glycol. In contrast, Comparative Examples 1 and 2 are 1,5-pentanediol and 1,6-hexanediol, respectively.
The solution viscosity before curing in Example 1 is extremely low with respect to the solution viscosities of Comparative Examples 1 and 2, and workability such as coating properties is extremely high. Furthermore, the cured film obtained in Example 1 has excellent breaking strength and breaking elongation as compared with the cured films of Comparative Examples 1 and 2, and has the highest pencil hardness and the highest wear resistance. Has physical properties.

  From these results, the use of a polycarbonate polyol containing neopentyl glycol as a constitutional unit and having crosslinking points at both ends makes the active energy ray-curing weight extremely low in solution viscosity compared to the case of using other polycarbonate polyols. It can be seen that a coalescence composition can be obtained, and that a cured film excellent in mechanical strength, wear resistance and hardness can be formed by irradiation of the active energy ray-curable polymer composition with active energy rays. .

It is generally known that the viscosity of a polycarbonate diol or the viscosity of an active energy ray-curable polymer composition containing a urethane (meth) acrylate oligomer based on the viscosity varies depending on the composition of the polycarbonate diol. . For example, rather than crystalline polycarbonate diol of 1,6-hexanediol alone, amorphous polycarbonate diol such as 1,6-hexanediol and 1,5-pentanediol or 3-methyl-1,5-pentanediol This type of copolymer generally has a lower viscosity. However, cured films of urethane (meth) acrylate oligomers based on the above copolymerization type are generally low in mechanical strength, for example, breaking strength and breaking elongation, and have no physical properties such as hardness and wear resistance. It is not satisfactory.
On the other hand, when the polycarbonate diol containing the structure (A) such as neopentyl glycol of the present invention is used as a raw material, the viscosity of the active energy ray-curable polymer composition containing the urethane (meth) acrylate oligomer obtained is obtained. In addition to being extremely low in coating properties and workability, the cured film obtained by irradiation with active energy rays is surprisingly a raw material made from crystalline 1,6-hexanediol polycarbonate diol. It became clear that it had extremely superior mechanical strength, hardness and wear resistance.

  The active energy ray-curable polymer composition of the present invention has a low solution viscosity and excellent workability, and a cured film that is more excellent in mechanical strength, hardness, and abrasion resistance can be easily obtained by a simple method of irradiation with active energy rays. For example, in the field of surface protection of a substrate with a cured film, further improvement in both the workability of forming the cured film and the performance of the cured film is expected.

Claims (7)

An active energy ray-curable polymer composition containing a urethane (meth) acrylate oligomer which is a reaction product of a raw material containing (1) polyisocyanate, (2) polycarbonate diol, and (3) hydroxyalkyl (meth) acrylate In
The (2) polycarbonate diol is produced by a transesterification reaction between a diol compound giving a repeating unit represented by the following formula (A) and the following formula (B) and a diaryl carbonate, and the following conditions ( An active energy ray-curable polymer composition comprising at least a polycarbonate diol satisfying i) to (iii).
(I) A repeating unit represented by the following formula (A) (hereinafter simply referred to as (A)) and a repeating unit represented by the following formula (B) having a structure other than (A) (hereinafter simply referred to as (B) )), Having hydroxyl groups at both ends of the polymer chain, and the ratio of (A) and (B) contained in the polymer is (A) / (B) = 99/1 to 1/99 in molar ratio. is there.
(Ii) The number average molecular weight is 500 or more and 10,000 or less.
(Iii) The following formula (a) is satisfied.
{(Number of moles of (A) at the polymer terminal) / (sum of the number of moles of (A) at the polymer terminal and the number of moles of (B))} / {(number of moles of (A) in the polymer) / (polymer The sum of the number of moles of (A) and the number of moles of (B))}> 1.2 (a)

(In the above formula, n is 0 or 1. R ₁ and R ₂ are each independently selected from the group consisting of alkyl groups, aryl groups, alkenyl groups, alkynyl groups, and alkoxy groups having 1 to 15 carbon atoms. And may have an oxygen atom, a sulfur atom, a nitrogen atom, a halogen atom or a substituent containing these in the range of the carbon number, and X and Y each independently contain a hetero atom. Represents a good divalent group having 1 to 20 carbon atoms.)   2. The active energy ray-curable polymer composition according to claim 1, wherein the molecular weight between calculated network cross-linking points is 500 to 10,000.   3. The active energy ray-curable heavy according to claim 1, wherein the raw material further contains a high-molecular-weight polyol having a number average molecular weight of 500 or more other than polycarbonate diol satisfying the conditions (i) to (iii). Combined composition.   The active energy ray-curable polymer composition according to any one of claims 1 to 3, wherein the raw material further contains a low molecular weight polyol having a molecular weight of less than 500.   The urethane (meth) acrylate-based oligomer has a structure obtained by reacting a urethane prepolymer having an isocyanate group at a terminal and the (3) hydroxyalkyl (meth) acrylate with a urethane bond, The active energy ray-curable polymer composition according to any one of claims 1 to 4, wherein the (1) polyisocyanate and the (2) polycarbonate diol are polymerized by a urethane bond.   The cured film formed by irradiating an active energy ray to the active energy ray-curable polymer composition as described in any one of Claims 1 thru | or 5. The laminated body which has a layer which consists of a cured film of Claim 6 on a base material.