JP2016199714A - Active energy ray-curable polymer composition, cured film using the same, and laminate having the cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable polymer composition which forms a cured film having excellent flexibility while having high hardness after active energy ray curing.SOLUTION: The active energy ray-curable polymer composition contains: a polyurethane (meth)acrylate-based oligomer which is a reaction product of raw materials including a polycarbonate diol containing a repeating unit represented by formula (A), a polyisocyanate, and a hydroxyalkyl (meth)acrylate; and an active energy ray-reactive monomer. The polyurethane (meth)acrylate-based oligomer and the active energy ray-reactive monomer are contained in amounts of 1-45 mass% and 55-99 mass%, respectively, based on 100 mass% of the active energy ray-curable polymer composition.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable polymer composition containing a polyurethane (meth) acrylate oligomer having a polycarbonate skeleton and an active energy ray-reactive monomer, and curing obtained by irradiating the composition with active energy rays. The present invention relates to a film and a laminate having the cured film.

  The active energy ray-curable polymer composition has the property of being polymerized and cured in a short time by an active energy ray such as ultraviolet rays, generally excellent in transparency, toughness, flexibility, scratch resistance, It is possible to have excellent characteristics such as chemical resistance. From this point, it is used in various fields such as a coating agent for plastics and glass, a molding agent for lens, a sealing agent, and an adhesive.

  In recent years, processing of base materials with complex shapes such as electronic paper and mobile phones has been demanded, and it has become necessary to have a cured film having flexibility while being able to prevent scratches with high hardness. .

  JP-A-2009-62499 (Patent Document 1) discloses 2-butyl-2-ethyl-1,3-propanediol as an ultraviolet curable resin composition that provides a hard coat film having high hardness and high flexibility. An ultraviolet curable resin composition containing urethane acrylate obtained by reacting 1,3-bis (isocyanatomethyl) cyclohexane and then reacting pentaerythritol triacrylate and tetraester acrylate is disclosed. However, the cured film obtained by irradiating this ultraviolet curable resin composition with ultraviolet rays has a problem that it has high hardness but insufficient flexibility.

  On the other hand, as an energy ray-curable resin composition that gives a coating film excellent in chemical resistance and flexibility, Japanese Patent Application Laid-Open No. 2009-227915 (Patent Document 2) includes an organic polyisocyanate and an alicyclic structure. An energy ray curable resin composition containing a urethane acrylate obtained by reacting a polycarbonate polyol having a polymer polyol with a (meth) acrylate containing one or more hydroxyl groups in the molecule is disclosed. However, the coating material using this energy beam curable resin composition has good flexibility when applied to a film or the like, but has a problem that its hardness is insufficient and the surface is easily damaged.

  Moreover, as an active energy ray-curable polymer composition from which a cured film having excellent stain resistance and hardness can be obtained, International Publication No. 2011-129377 (Patent Document 3) includes specific polycarbonate diol, polyisocyanate, And an active energy ray-curable polymer composition containing a urethane (meth) acrylate oligomer that is a reaction product of a raw material containing hydroxyalkyl (meth) acrylate. However, the cured film obtained by irradiating the active energy ray-curable polymer composition with active energy rays has a problem that the hardness is not sufficient and the surface is easily damaged.

JP 2009-62499 A JP 2009-227915 A International Publication No. 2011-129377

  The present invention has been made in view of the above-described problems of the prior art, and is an active energy ray-curable polymer capable of forming a cured film having high hardness and excellent flexibility after active energy ray curing. It aims at providing the laminated body which has a composition and such a cured film.

  As a result of intensive studies to achieve the above object, the present inventors have determined that an active energy containing a specific polyurethane (meth) acrylate oligomer having a specific polycarbonate skeleton and an active energy ray-reactive monomer in a specific ratio. By using the linear curable polymer composition, it has been found that a cured film having high flexibility but excellent flexibility and good adhesion to a substrate can be obtained. It came to complete.

  That is, the active energy ray-curable polymer composition of the present invention has the following general formula (A):

And the following general formula (B):

(In formula (B), X represents a C1-C15 divalent organic group which may contain a hetero atom.)
Activity containing a polyurethane (meth) acrylate oligomer which is a reaction product of a raw material containing polycarbonate diol, polyisocyanate, and hydroxyalkyl (meth) acrylate containing a repeating unit represented by An energy ray curable polymer composition comprising:
The polyurethane (meth) acrylate oligomer is contained at 1% by mass to 45% by mass with respect to 100% by mass of the active energy ray-curable polymer composition, and the active energy ray-reactive monomer is 55% by mass or more. It contains 99 mass% or less, It is characterized by the above-mentioned.

  The active energy ray-curable polymer composition of the present invention contains the polyurethane (meth) acrylate oligomer in an amount of 5% by mass to 45% by mass with respect to 100% by mass of the active energy ray-curable polymer composition. And it is preferable to contain the said active energy ray reactive monomer 55 mass% or more and 95 mass% or less.

  In the active energy ray-curable polymer composition of the present invention, the active energy ray-reactive monomer includes aromatic vinyl monomers, vinyl ester monomers, vinyl ethers, allyl compounds, and (meth) acrylamides. And at least one selected from the group consisting of (meth) acrylates. The polycarbonate diol contains 10% by mass or more of the repeating unit represented by the formula (A), the number average molecular weight of the polycarbonate diol is 500 or more and 5,000 or less, and the average hydroxyl group per molecule. Those having a number of 2.2 or less are preferred. The active energy ray-curable polymer composition of the present invention preferably further contains an active energy ray polymerization initiator.

  The cured film of the present invention is obtained by irradiating the active energy ray-curable polymer composition of the present invention with active energy rays, and the laminate of the present invention comprises a layer comprising such a cured film. It is what you have.

  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 the (meth) acryloyl group and (meth) acrylic acid.

  According to the present invention, the active energy ray-curable heavy weight that can form a cured film that is excellent in flexibility while being high in hardness and excellent in adhesion to the substrate by irradiation with active energy rays. A united composition and a laminate having such a cured film can be provided.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

<Active energy ray-curable polymer composition>
The active energy ray-curable polymer composition of the present invention includes a polycarbonate diol, a polyisocyanate, and a hydroxy group containing a repeating unit represented by the following general formula (A) and a repeating unit represented by the following general formula (B). An active energy ray-curable polymer composition comprising a polyurethane (meth) acrylate oligomer that is a reactant of a raw material containing an alkyl (meth) acrylate, and an active energy ray-reactive monomer,
The polyurethane (meth) acrylate oligomer is contained at 1% by mass to 45% by mass with respect to 100% by mass of the active energy ray-curable polymer composition, and the active energy ray-reactive monomer is 55% by mass or more. It is contained at 99% by mass or less.

  In formula (B), X represents a C1-C15 divalent organic group which may contain a hetero atom.

[Polyurethane (meth) acrylate oligomer]
The polyurethane (meth) acrylate oligomer used in the present invention includes a polycarbonate diol, a polyisocyanate, and a hydroxyl group containing the repeating unit represented by the general formula (A) and the repeating unit represented by the general formula (B). It is a raw material reactant containing an alkyl (meth) acrylate. Such polyurethane (meth) acrylate oligomers may be used alone or in combination of two or more. Below, each component of the raw material of a polyurethane (meth) acrylate type oligomer is demonstrated.

(Polycarbonate diol)
The polycarbonate diol used in the present invention is a repeating unit represented by the general formula (A) (hereinafter sometimes abbreviated as “structure (A)”) and a repeating unit represented by the general formula (B) (hereinafter referred to as “the structural unit (A)”). "May be abbreviated as" structure (B) "). The polycarbonate diol used in the present invention is preferably one produced from a diol and a carbonic acid diester as raw materials and using a transesterification catalyst.

  Examples of the diol include isosorbide and at least one of its stereoisomers, isomannide and isoidid, and a diol having 1 to 15 carbon atoms which may contain a hetero atom. Examples of the carbonic acid diester include alkyl carbonate, aryl carbonate, and alkylene carbonate.

  Examples of the transesterification catalyst include simple metals that are generally considered to have transesterification ability and metal compounds such as hydroxides and salts. Of these, acetates, carbonates and hydroxides of Group 1 metals of the periodic table and Group 2 metals of the periodic table are preferred, and catalysts using Group 2 metals of the periodic table are more preferred. Although the catalyst used at the time of manufacture may remain in the polycarbonate diol, the subsequent polyurethane-forming reaction may be accelerated more than expected, and it is preferable that the catalyst does not remain. From such a viewpoint, the amount of catalyst remaining in the polycarbonate diol is preferably 100 ppm by mass or less as the content in terms of catalyst metal. The lower limit of the residual amount of the catalyst is better, but may be 0.1 mass ppm or more from the viewpoint of simplifying the production method.

  The polycarbonate diol used in the present invention has a number average molecular weight of 500 or more and 5,000 or less from the viewpoint that the viscosity of the polyurethane (meth) acrylate oligomer is low and easy to handle and the mechanical strength of the cured product. preferable. The polycarbonate diol has at least two hydroxyl groups in the molecular chain, and preferably one hydroxyl group at each end of the molecular chain. Such polycarbonate diol may be used individually by 1 type, or may use 2 or more types together.

{Structure (A)}
The first structural feature of the structure (A) according to the present invention is that it is a rigid structure having a small flexibility with two furan rings condensed. For this reason, in the polycarbonate diol used in the present invention, In this structure (A), rigidity is expressed. The second feature is that the carbonate group is directly bonded to the condensed furan ring without a free-rotatable group such as a methylene group. Therefore, the degree of freedom is low in this part, and it is extremely rigid. It is in the structure. The third feature is that two hydrophilic furan rings having a high density are arranged. For this reason, it has an affinity for a polar group such as a water molecule and has a high hydrophilic property. Have.

  In addition, the polycarbonate diol used in the present invention preferably has a ratio of the number of the molecular chain terminal of an alkyloxy group or an aryloxy group of 5% or less with respect to the total number of terminals of the molecular chain, The ratio of the number of molecular chain ends that are alkyloxy groups or aryloxy groups is 5% or less with respect to the total number of terminals of the molecular chain, and 95% or more of both ends of the molecular chain are hydroxyl groups Those are more preferred. In the polyurethane reaction, the hydroxyl group can react with the polyisocyanate.

  The structure (A) may be continuous in the polycarbonate diol, may exist at regular intervals, or may be unevenly distributed. The content of the structure (A) in the polycarbonate diol is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 40% by mass or more from the viewpoints of rigidity and hydrophilicity described above. Introducing a structure other than the structure (A) into the molecular chain, in addition to the effects brought about by the rigidity, hydrophilicity, etc. described above, the regularity of the polycarbonate diol is disturbed, so the melting point and viscosity are lowered. And the effect that handling property improves is acquired.

{Structure (B)}
X in the general formula (B) representing the structure (B) is a divalent group having 1 to 15 carbon atoms which may contain a hetero atom, and is a linear or branched chain group, cyclic group, Any structure may be included. The number of carbons that are elements constituting X is preferably 10 or less, and more preferably 6 or less. Examples of the hetero atom that may be contained in X include an oxygen atom, a sulfur atom, and a nitrogen atom, and an oxygen atom is preferable from the viewpoint of chemical stability. Specific examples of the group X include groups generated when the compounds exemplified below are used as the compounds giving the structure (B) during the production of the polycarbonate diol used in the present invention. Of these, groups obtained by reacting preferred compounds are preferred.

  The structure (B) may be continuous in the polycarbonate diol, may exist at regular intervals, or may be unevenly distributed. The content of the structure (B) in the polycarbonate diol is preferably 80% by mass or less, from the viewpoint of improving the handling property by disturbing the regularity of the polycarbonate diol and lowering the melting point and the viscosity. The following is more preferable, 40% by mass or less is further preferable, and 20% by mass or less is particularly preferable.

{Ratio of structure (A) to structure (B)}
The ratio of the structure (A) to the structure (B) constituting the molecular chain of the polycarbonate diol used in the present invention (hereinafter sometimes referred to as “(A) / (B) ratio”) is usually a molar ratio. Structure (A) / Structure (B) = 99/1 to 1/99. By introducing the structure (B) into the molecular chain, the regularity of the polycarbonate diol is disturbed, so that the melting point and the viscosity are lowered and the handling property is improved. It is the portion of the structure (A) that mainly brings about the effects of the present invention such as rigidity and hydrophilicity described above, and if the proportion of the structure (A) in the polycarbonate diol used in the present invention is too small, the effects are obtained. You may not get enough. The ratio A) / (B) is preferably 99/1 to 10/90, more preferably 80/20 to 20/80, and still more preferably 70/30 to 30/70.

  In the polycarbonate diol used in the present invention, the ratio of the structure (A) / structure (B) at the molecular chain terminal, that is, the structure represented by the general formula (A) and a hydrogen atom, an alkyloxy group or an aryloxy group A portion where a molecular chain end is formed by a combination of the above, a portion where a molecular chain end is formed by a combination of the structure represented by the general formula (B) and a hydrogen atom, an alkyloxy group or an aryloxy group; The ratio (hereinafter, this ratio may be referred to as “terminal (A) / (B) ratio”) is preferably 95/5 to 20/80, more preferably 90/10 to 30/70, 80 / 20-40 / 60 is still more preferable. If the molecular chain terminal has more structure (B) parts than this range, the designed characteristics such as hardness may not be obtained.

  Further, the ratio of the structure (A) of the molecular chain terminal to the sum of the number of structures (A) and the structure (B) of the molecular chain terminal obtained by the following formula (I), and the structure ( The ratio of the structure (A) in all the molecular chains to the total of the number of A) and the number of the structure (B) (hereinafter sometimes referred to as “terminal (A) ratio (I)”) is particularly limited. However, it is usually 1.1 or more (preferably 1.2 or more, more preferably 1.3 or more, particularly preferably 1.4 or more), and usually 5.0 or less (preferably 3.0 or less More preferably, it is 2.0 or less, more preferably 1.9 or less, and particularly preferably 1.8 or less. When the terminal (A) ratio (I) is less than the lower limit, a practical urethanization reaction rate may not be obtained in the industrial implementation. On the other hand, when the ratio exceeds the upper limit, the urethanization reaction may occur. Due to the speed being too high, the urethanization reaction may proceed too much and the designed physical properties such as hardness may not be obtained. The terminal (A) ratio (I) can be adjusted by the ratio of the diol as the raw material of the structure (A) and the structure (B), the type and amount of catalyst, the maximum reaction temperature, and the reaction time.

{Raw material monomer}
As will be described later, the polycarbonate diol used in the present invention is produced using diol and carbonic acid diester as raw materials.

(Carbonated diester)
The carbonic acid diester that can be used is not limited as long as the effects of the present invention are not lost, and examples thereof include alkyl carbonates, aryl carbonates, and alkylene carbonates. Of these, the use of aryl carbonate has the advantage that the reaction proceeds rapidly. On the other hand, when aryl carbonate is used as a raw material, phenols having a high boiling point are by-produced, but it is preferable that the residual amount of phenols in the polycarbonate diol product is smaller. This is because phenols are monofunctional compounds that can be polymerization inhibitors during polyurethane formation and are also stimulating substances.

  Specific examples of the dialkyl carbonate, diaryl carbonate, and alkylene carbonate of the carbonic acid diester that can be used in the production of the polycarbonate diol used in the present invention are as follows.

  Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate, and ethyl isobutyl carbonate. Among them, dimethyl carbonate and diethyl carbonate are preferable. Examples of the diaryl carbonate include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, di m-cresyl carbonate, and among them, diphenyl carbonate is preferable. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, and 1,2-pentylene. Carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, neopentyl carbonate, etc. Among these, ethylene carbonate is preferable. These may be used alone or in combination of two or more. Among these, diaryl carbonate is preferable because it is rich in reactivity and efficient in industrial production, and diphenyl carbonate that is easily available at low cost as industrial raw material is more preferable.

(Diol)
On the other hand, among the diols, specific examples of diols that give the structure (A) and the structure (B) contained in the polycarbonate diol used in the present invention are shown below.

(Raw material diol of structure (A))
Examples of the raw material diol that gives the structure (A) include isosorbide and its stereoisomers such as isomannide and isoidide, and these may be used alone or in combination of two or more. Among them, isosorbide that is easily obtained by a dehydration reaction of sorbitol and is commercially available in an industrial amount is preferable.

(Raw material diol of structure (B))
Examples of the raw material diol that gives the structure (B) include diols having 1 to 15 carbon atoms that may contain the above heteroatoms, and diols having 2 to 10 carbon atoms are preferable. For example,
Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Terminal diols of linear hydrocarbons such as diol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol;
Linear diols having an ether group such as diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol;
Thioether diols such as bishydroxyethyl thioether;
2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-butyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl- 2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-pentyl-2-propyl-1,3-propanediol, 2-pentyl-2-propyl-1,3 -Propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 2,2,4,4-tetramethyl-1,5-pentanediol, 2-ethyl- Diols having a branched chain such as 1,6-hexanediol and 2,2,9,9-tetramethyl-1,10-decanediol;
1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 1,4-dihydroxy Diols having an alicyclic structure such as ethylcyclohexane, 4,4′-isopropylidene dicyclohexanol, 4,4′-isopropylidenebis (2,2′-hydroxyethoxycyclohexane), norbornane-2,3-dimethanol Kind;
2,5-bis (hydroxymethyl) tetrahydrofuran, 3,4-dihydroxytetrahydrofuran, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5. 5] Undecane (cas number: 1455-42-1), 2- (5-ethyl-5-hydroxymethyl-1,3-dioxan-2-yl) -2-methylpropan-1-ol (cas number: 59802) Diols containing a cyclic group having a hetero atom in the ring, such as -10-7);
Nitrogen-containing diols such as diethanolamine and N-methyl-diethanolamine;
And sulfur-containing diols such as bis (hydroxyethyl) sulfide. These diols may be used alone or in combination of two or more.

  Among these diols, industrial hydrocarbons, the obtained polycarbonate diol and the cured product obtained by curing the active energy ray-curable polymer composition are excellent in physical properties, and therefore, terminal diols of linear hydrocarbons. As ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and the like, a chain having an ether group is preferable. As the diol, diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol, polytetramethylene glycol and the like are preferable. As the diol having a branched chain, 2-methyl-1,3-propanediol, 2-ethyl-1 , 3-propanediol, 2,2-dimethyl- , 3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl -1,5-pentanediol, 2,2,4,4-tetramethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol and the like are preferable, and diols having an alicyclic structure are preferable. 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2'-bis (4-hydroxycyclohexyl) propane, 4,4'- Preferred are isopropylidene dicyclohexanol, norbornane-2,3-dimethanol, etc., having a hetero atom in the ring Examples of diols containing a group include 3,4-dihydroxytetrahydrofuran, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (Cas number: 1455-42-1), 2- (5-ethyl-5-hydroxymethyl-1,3-dioxan-2-yl) -2-methylpropan-1-ol (cas number: 59802-10- 7) and the like are preferable. Among these, from the viewpoint of mechanical strength and industrial availability of the obtained cured film, diols having 4 to 6 carbon atoms are more preferable, and 1,4-butanediol, 1,6-hexanediol, 3- Methyl-1,5-pentanediol is particularly preferred.

(Diol for structure (A))
The polycarbonate diol used in the present invention is characterized in that it contains the structure (A) and the structure (B). The diols giving this structure (A) (hereinafter referred to as “structure (A) diol”). ) May be unstable and requires caution when stored and used. For example, since isosorbide is gradually oxidized in the presence of oxygen, it is important to use an oxygen scavenger or to put it in a nitrogen atmosphere to prevent decomposition due to oxygen during storage and handling during production. is there. It is also necessary to prevent moisture from entering. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when polycarbonate diol is produced using isosorbide containing these decomposition products, the resulting polycarbonate diol may be colored or the physical properties may be significantly deteriorated. In addition, the polymerization reaction may be affected, and a polymer having a target molecular weight may not be obtained.

  As these countermeasures, methods described in publicly known documents can be arbitrarily adopted. For example, Japanese Patent Application Laid-Open No. 2009-161745 defines a preferable amount of formic acid contained in a raw material dihydroxy compound such as isosorbide used when producing a polycarbonate. If a dihydroxy compound of a specified amount or less is used, the physical properties It is said that a good polycarbonate can be obtained. The same applies to the production of the polycarbonate diol used in the present invention. The amount of formic acid contained in the diol for structure (A) to be used is preferably 20 ppm or less, more preferably 10 ppm or less, and more preferably 5 ppm or less. Is more preferable. Although it does not specifically limit as a minimum, 1 ppm or more is preferable and 0.1 ppm or more is more preferable.

  Moreover, these diols for structure (A) tend to lower the pH because they produce acidic substances such as formic acid when they are oxidatively degraded. Therefore, pH can also be used as an index for evaluation of usable diol for structure (A). For example, the method described in WO09 / 057609, that is, a method of measuring with a pH meter as a 40% aqueous solution of a raw material diol can be adopted as the pH. The pH of the 40% aqueous solution of the structure (A) diol necessary for producing the polycarbonate diol used in the present invention is usually pH 3 or more (preferably pH 4 or more, more preferably pH 5 or more), and usually pH 11 Or less (preferably pH 10 or less).

  When the diol for structure (A) is oxidized and deteriorated, a peroxide is generated. This peroxide is preferably less because it may cause coloration during the production of the polycarbonate diol used in the present invention or during the urethanization reaction. The amount of the peroxide in the structure (A) diol is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 3 ppm or less, and particularly preferably 1 ppm or less with respect to the mass of the structure (A) diol. Although it does not specifically limit as a minimum, 0.01 ppm or more is preferable.

  When the diol for structure (A) contains a periodic table group 1 metal and / or a periodic table group 2 metal compound, the reaction rate at the time of converting the polycarbonate diol into a polyurethane is further increased during the polycarbonate formation reaction. It may have an effect. Therefore, the content of the periodic table group 1 metal and / or the periodic table group 2 metal compound in the diol for structure (A) is preferably smaller, and the mass ratio of the metal to the diol mass for structure (A) Is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 3 ppm or less, particularly preferably 1 ppm or less, and most preferably no periodic group 1 metal and / or group 2 metal compound (0 ppm). .

  When a halogen component such as chloride ion or bromide ion is contained in the diol for structure (A), it may affect the reaction during the polycarbonate formation reaction, and further the reaction when the obtained polycarbonate diol is converted into a polyurethane, Since it may cause coloring, it is preferable that the content is small. The content of the halogen component in the diol for the structure (A) is preferably 10 ppm or less, more preferably 5 ppm or less, and particularly preferably 1 ppm or less as the halogen content with respect to the mass of the diol for the structure (A).

  The structure (A) diol that deteriorates due to oxidation or the like, or contains the above impurities, can be purified by, for example, distillation, etc., so that it is distilled before use for polymerization and is in the above range. Is possible. In order to prevent oxidative degradation again after distillation, it is also effective to add a stabilizer. Specific stabilizers can be used without limitation as long as they are generally used as antioxidants for organic compounds, and include butylhydroxytoluene, butylhydroxyanisole, 2,6-di-t- Butyl-4-methylphenol, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -6-di-t-pentylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer ( Registered trademark) GS) and the like, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [D, f] [1, 3, 2] dioxaphosphepine (trade name Sumilizer (registered trademark) GP, manufactured by Sumitomo Chemical Co., Ltd.), bis (2,4-di-t-butyl) Phenyl) phosphorus-based stabilizer such pentaerythritol phosphite as examples.

{Molecular weight and molecular weight distribution}
As the number average molecular weight of the polycarbonate diol, good workability due to an appropriate viscosity of the polyurethane (meth) acrylate oligomer, mechanical strength of a cured product obtained by curing the active energy ray-curable polymer composition, and From the viewpoint of stain resistance, 500 or more is preferable, 800 or more is more preferable, 1,000 or more is more preferable, 5,000 or less is preferable, 3,000 or less is more preferable, and 2,000 or less is more preferable. 1,500 or less is particularly preferable. As the number average molecular weight of the polycarbonate diol decreases, the workability tends to improve and the mechanical strength and stain resistance of the cured product tend to improve. In addition, as the number average molecular weight of the polycarbonate diol increases, the flexibility of following the deformation during the three-dimensional processing of the cured product tends to improve.

  The molecular weight distribution (Mw / Mn) of the polycarbonate diol used in the present invention is not particularly limited, but is usually 1.5 or more (preferably 2.0 or more), and usually 3.5 or less (preferably 3.0). The following). If an attempt is made to produce a polycarbonate diol having a molecular weight distribution below the lower limit, an advanced purification operation such as removal of oligomers may be required. If the molecular weight distribution exceeds the upper limit, the activity produced using this polycarbonate diol may be required. The physical properties of a cured product obtained by curing the energy beam curable polymer composition tend to deteriorate, such as being hardened at low temperatures and poor elongation. Here, Mw is a weight average molecular weight, Mn is a number average molecular weight, and can be usually determined by measurement by gel permeation chromatography (GPC).

{Ratio of the number of molecular chain ends that are alkyloxy groups or aryloxy groups / hydroxyl value}
In the polycarbonate diol used in the present invention, the terminal structure of the polymer is basically a hydroxyl group. However, the polycarbonate diol product obtained by the reaction of diol and carbonic acid diester may have a structure in which some polymer terminals are not hydroxyl groups as impurities. As specific examples of the structure, the molecular chain terminal is an alkyloxy group or an aryloxy group, and many are structures derived from a carbonic acid diester. For example, when diphenyl carbonate is used as the carbonic acid diester, phenoxy group (PhO-) is used as the aryloxy group, methoxy group (MeO-) is used as the alkyloxy group when dimethyl carbonate is used, and ethoxy group is used when diethyl carbonate is used. When (EtO-), ethylene carbonate is used, a hydroxyethoxy group (HOCH ₂ CH ₂ O-) may remain as a terminal group (where Ph represents a phenyl group, Me represents a methyl group, Et represents an ethyl group).

  In the present invention, the proportion of the structure in which the molecular chain terminal contained in the polycarbonate diol product is an alkyloxy group or aryloxy group is preferably 5 mol% or less of the total number of terminal groups. It is more preferably at most mol%, particularly preferably at most 1 mol%. The lower limit of the ratio of the number of terminals of this molecular chain being an alkyloxy group or an aryloxy group is not particularly limited, but is preferably 0.01 mol% or more, more preferably 0.001 mol% or more, and 0 mol%. The above is most preferable. When the ratio of the alkyloxy group or aryloxy end group is large, there may be a problem that the degree of polymerization does not increase when the polyurethane-forming reaction is carried out. As described above, the polycarbonate diol used in the present invention has a ratio of the number of molecular chain ends that are alkyloxy groups or aryloxy groups within the above range, and both terminal groups of the molecular chain are basically hydroxyl groups. There is a structure in which this hydroxyl group can react with isocyanate during the polyurethane-forming reaction.

  The hydroxyl value (OH value) of the polycarbonate diol is preferably 20 mgKOH / g or more from the viewpoint of mechanical strength and stain resistance of a cured product obtained by curing the active energy ray-curable polymer composition, and 35 mgKOH / G or more is more preferable, 55 mgKOH / g or more is further more preferable, and 75 mgKOH / g or more is particularly preferable. From the same viewpoint, 250 mgKOH / g or less is preferable, and 150 mgKOH / g or less is more preferable. When the hydroxyl value of the polycarbonate diol is decreased, the flexibility that can follow the deformation during the three-dimensional processing of the cured product tends to be improved. When the hydroxyl value of the polycarbonate diol is increased, the mechanical strength and stain resistance of the cured product tend to be improved. In addition, the hydroxyl value (OH value) of polycarbonate diol can be measured by the method mentioned later.

  The average number of hydroxyl groups per molecule of the polycarbonate diol is preferably 2.2 or less, and more preferably 2.1 or less, from the viewpoint of suppressing gelation during the production of the polyurethane (meth) acrylate oligomer. If the average number of hydroxyl groups per molecule of the polycarbonate diol exceeds the upper limit, gelation occurs during the production of the polyurethane (meth) acrylate oligomer, which may damage not only the polyurethane (meth) acrylate oligomer but also the reaction vessel, In addition, the obtained active energy ray-curable polymer composition is not preferable because it contains a gel and has high viscosity, resulting in poor applicability. Further, the lower limit of the average number of hydroxyl groups per molecule of the polycarbonate diol is not particularly limited, but the molecular weight of the polyurethane (meth) acrylate oligomer is within the target range, and the active energy ray-curable heavy weight containing the oligomer is included. From the viewpoint that the cured film obtained from the combined composition has an excellent balance between three-dimensional processing characteristics and stain resistance, 1.0 or more is preferable, 1.5 or more is more preferable, and 1.8 or more is preferable. Is more preferable. If the average number of hydroxyl groups per molecule of the polycarbonate diol is less than the lower limit value, the molecular weight tends to be difficult to react with the diisocyanate, and the polyurethane (meth) acrylate oligomer having the target molecular weight cannot be obtained. There is a possibility that a cured film obtained from the active energy ray-curable polymer composition containing the oligomer cannot be made to have an excellent balance between three-dimensional processing characteristics and stain resistance. That is, the average number of hydroxyl groups per molecule of the polycarbonate diol is preferably within 2.0 ± 0.2, more preferably within 2.0 ± 0.1, and most preferably 2.0. The average number of hydroxyl groups per molecule of polycarbonate diol can be calculated from the number average molecular weight and hydroxyl value obtained by the method described later.

{Ether structure}
The polycarbonate diol used in the present invention basically has a structure in which a raw material diol is polymerized by a carbonate group. However, depending on the production method, a part of the ether structure other than the structures (A) and (B) described above may be mixed in, and if the amount thereof is increased, the weather resistance and heat resistance may be reduced. Therefore, it is desirable to produce such that the proportion of the ether structure other than structures (A) and (B) does not become excessive. Structures contained in the molecular chain of the polycarbonate diol used in the present invention in that the ether structure other than the structures (A) and (B) in the polycarbonate diol is reduced to ensure the properties such as weather resistance and heat resistance. The ratio of the ether bond and carbonate bond other than (A) and (B) is preferably 2/98 or less, more preferably 1/99 or less, and particularly preferably 0.5 / 99.5 or less in terms of molar ratio.

{Viscosity / Solvent solubility}
The polycarbonate diol used in the present invention usually exhibits a property from a liquid to a waxy white turbid solid at around room temperature. However, when heated, the viscosity can be lowered and the handling becomes easy. It can also be dissolved in an amide solvent such as dimethylformamide or dimethylacetamide, an ester solvent such as γ-butyrolactone, or a sulfoxide solvent such as dimethyl sulfoxide, which may facilitate transfer and reaction. The property of the polycarbonate diol used in the present invention is usually a liquid to white waxy solid at room temperature as described above, and the property varies depending on the temperature. For example, in terms of viscosity, the viscosity of the polycarbonate diol used in the present invention at 40 ° C. is preferably 0.1 Pa · s or more, more preferably 1 Pa · s or more, further preferably 5 Pa · s or more, and 108 Pa · s. s or less is preferable, 107 Pa · s or less is more preferable, and 106 Pa · s or less is particularly preferable.

{APHA value}
The color of the polycarbonate diol used in the present invention is preferably in a range that does not affect the hue of the resulting polyurethane (meth) acrylate oligomer, and the degree of coloring is expressed in terms of Hazen color number (based on JIS K0071-1) The value (hereinafter referred to as “APHA value”) is not particularly limited, but is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less.

{Impurity phenol content}
The content of the phenols contained in the polycarbonate diol used in the present invention is not particularly limited, but is preferably less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and 001 mass% or less is still more preferable. This is because phenols are monofunctional compounds and can be a polymerization inhibitor during polyurethane formation, and are stimulating substances.

{Impurity carbonic acid diester content}
In the polycarbonate diol product used in the present invention, the carbonic acid diester used as a raw material during the production may remain, but the residual amount of the carbonic acid diester in the polycarbonate diol used in the present invention is not particularly limited. However, less is preferable, 5 mass% or less is preferable, 3 mass% or less is more preferable, and 1 mass% or less is still more preferable. If the carbonic acid diester content of the polycarbonate diol is too high, the reaction during polyurethane formation may be inhibited. On the other hand, the lower limit is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.01% by mass or more, and particularly preferably 0% by mass or more.

{Impurity diol content}
In the polycarbonate diol used in the present invention, the raw material diol used during production may remain. The residual amount of the raw material diol in the polycarbonate diol used in the present invention is not particularly limited, but is preferably less, preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less, 1 mass% or less is still more preferable, 0.1 mass% or less is especially preferable, and 0.05 mass% or less is the most preferable. When at least one diol selected from isosorbide, isomannide, and isoidide (hereinafter sometimes abbreviated as “isosorbides”) is used as the raw material diol, the remaining amount of isosorbides in the polycarbonate diol is as follows: Less is preferable, 10 mass% or less is preferable, 5 mass% or less is more preferable, 3 mass% or less is further preferable, 1 mass% or less is still more preferable, 0.1 mass% or less is particularly preferable, 0.01 The mass% or less is most preferable. When the residual amount of the raw material diol in the polycarbonate diol is large, the molecular length of the soft segment portion when the polyurethane (meth) acrylate oligomer is obtained may be insufficient.

  The diol that was the raw material of the polycarbonate diol can be identified by NMR measurement of the polycarbonate diol product or by NMR measurement or GC and LC measurement of the unreacted diol contained in the product. When it remains in a thing, it can identify from NMR measurement or GC and LC measurement. Moreover, the structure of the carbonic acid diester which was the raw material can also be estimated from the impurities such as alcohol components produced as a by-product when the carbonic acid diester reacts by NMR measurement or GC and LC measurement of the product.

{Impurity transesterification catalyst content}
When the polycarbonate diol used in the present invention is produced, a transesterification catalyst can be used as necessary in order to accelerate the polymerization as described later. In that case, the catalyst may remain in the obtained polycarbonate diol, but if too much catalyst remains, it becomes difficult to control the reaction during the polyurethane reaction, and the polyurethane reaction is accelerated more than expected. It may become a gel and a uniform polyurethane (meth) acrylate oligomer may not be obtained. The amount of catalyst remaining in the polycarbonate diol is not particularly limited, but from the viewpoint of obtaining a homogeneous polyurethane (meth) acrylate oligomer from the polycarbonate diol, the content in terms of catalyst metal is preferably 100 mass ppm or less, and 50 mass. More preferably, ppm or less is more preferable, 30 mass ppm or less is still more preferable, and 10 mass ppm or less is especially preferable. Examples of the remaining metal include catalytic active component metals having transesterification ability described below. The lower limit of the amount of catalyst remaining in the polycarbonate diol is not particularly limited, but the content in terms of catalyst metal is preferably 5 ppm by mass, more preferably 1 ppm by mass, still more preferably 0.1 ppm by mass, 0.01 mass ppm is particularly preferred. Usually, it is difficult to remove the catalyst used in the production of the polycarbonate diol after the production, and it is often difficult to make the amount of the remaining catalyst less than the lower limit of the usage amount described later. The amount of the catalyst in the polycarbonate diol can be adjusted by the amount of catalyst used at the time of production, catalyst isolation by filtration of the product, catalyst extraction using a solvent such as water, or the like.

{Impurity cyclic carbonate content}
The polycarbonate diol product may contain cyclic carbonate by-produced during production. For example, when 1,3-propanediol is used as the raw material diol, 1,3-dioxan-2-one or a compound obtained by forming a cyclic carbonate with two or more of these molecules as a cyclic compound is produced as a polycarbonate diol. May be included. These compounds are impurities that may cause side reactions in the polyurethane-forming reaction, so it is desirable to remove them as much as possible in the production stage. The content of these impurity cyclic carbonates contained in the polycarbonate diol used in the present invention is not particularly limited, but is preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less. .

{Urethaneization reaction rate}
The reaction rate in the urethanization reaction of the polycarbonate diol used in the present invention can be determined from the remaining NCO% according to the following method. That is, 0.2 g of the composition in the reaction is collected in an Erlenmeyer flask, and 10 ml of 0.1N dibutylamine is mixed and dissolved. Next, a few drops of bromophenol blue solution are added, titrated with 0.1N hydrochloric acid ethanol solution, and the remaining NCO% is determined by the following formula.
NCO% = (a−b) × 0.42 × f / x
(Where, a: titration of 0.1 N hydrochloric acid ethanol solution when titrating the composition before reaction, b: titration of 0.1 N hydrochloric acid ethanol solution when titrating the composition during reaction, f: 0.1N hydrochloric acid ethanol factor, x: sampling amount)
The reaction rate is determined from the obtained residual NCO% by the following formula.
Reaction rate (%) = (dc) / (de) × 100
(Wherein, c: remaining NCO% during reaction, d: remaining NCO% before reaction, e: remaining NCO% after reaction).

{Production method of polycarbonate diol}
The polycarbonate diol used in the present invention requires a raw material diol typified by isosorbide giving the above-mentioned structure (A), a diol such as a raw material diol giving the above-mentioned structure (B), and the above-mentioned carbonic acid diester. Accordingly, it can be produced by transesterification using a transesterification catalyst. For example, (i) at least one diol selected from isosorbide, isomannide, and isoidide, (ii) a diol having 1 to 15 carbon atoms that may contain a heteroatom, and (iii) a carbonic acid diester It can be produced by reacting in the presence of a catalyst. The manufacturing method will be described below.

(Transesterification catalyst)
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 catalytic metals include Group 1 metals of the periodic table such as lithium, sodium, potassium, rubidium and cesium; Group 2 metals of the periodic table such as magnesium, calcium, strontium and barium; Group 4 metals of the periodic table such as titanium and zirconium Periodic group 5 metal such as hafnium; periodic group 9 metal such as cobalt; periodic table 12 metal such as zinc; periodic group 13 metal such as aluminum; periodic group 14 metal such as germanium, tin, lead; Examples include periodic table 15 group metals such as antimony and bismuth; lanthanide metals such as lanthanum, cerium, europium, and ytterbium. Among these, from the viewpoint of increasing the transesterification reaction rate, periodic table group 1 metal, periodic table group 2 metal, periodic table group 4 metal, periodic table group 5 metal, periodic table group 9 metal, periodic table 12 metal, periodicity A Group 13 metal and a Group 14 metal are preferable, a Group 1 metal and a Group 2 metal are more preferable, and a Group 2 metal is more preferable. Among the group 1 metals of the periodic table, lithium, potassium, and sodium are preferable, lithium and sodium are more preferable, and sodium is still more preferable. Among the Group 2 metals of the periodic table, magnesium, calcium and barium are preferable, calcium and magnesium are more preferable, and magnesium is more preferable. These metals may be used as a single metal or as a metal compound such as a hydroxide or a salt. Examples of salts when used as a salt include halide salts such as chloride, bromide and iodide; carboxylates such as acetate, formate and benzoate; methanesulfonic acid, toluenesulfonic acid and trifluoro Examples thereof include sulfonates such as lomethanesulfonic acid; phosphorus-containing salts such as phosphates, hydrogen phosphates, and dihydrogen phosphates; acetylacetonate salts. The catalyst metal can also be used as an alkoxide such as methoxide or ethoxide.

  Among these, periodic table group 1 metal, periodic table group 2 metal, periodic table group 4 metal, periodic table group 5 metal, periodic table group 9 metal, periodic table 12 metal, periodic table group 13 metal, periodic table group 14 metal Preferred are acetates, nitrates, sulfates, carbonates, phosphates, hydroxides, halides, and alkoxides, and more preferred are acetates, carbonates, and hydroxides of Group 1 metals or Group 2 metals of the Periodic Table. Preferably, the periodic table group 2 metal acetate is more preferable. These metals and metal compounds may be used alone or in combination of two or more.

  The compounds using the Group 1 metals 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, benzoic acid Lithium, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate; disodium salt, bispotassium salt, cesium salt, dilithium salt of bisphenol A; Salt, potassium salt, cesium salt and lithium salt and the like.

  Examples of compounds using Group 2 metals of the periodic table include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, Examples thereof include strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium magnesium phosphate.

  Examples of compounds using Group 4 metal, Group 12 metal, and Group 14 metal of the periodic table include titanium alkoxides such as tetraethyl titanate, tetraisopropyl titanate, and tetra-n-butyl titanate; halides of titanium such as titanium tetrachloride; zinc acetate Zinc salts such as zinc benzoate and zinc 2-ethylhexanoate; tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide Tin compounds such as zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, and the like; lead compounds such as lead (II) acetate, lead (IV) acetate, and lead (IV) chloride.

{Use ratio of raw materials}
In the production of the polycarbonate diol used in the present invention, the amount of carbonic acid diester used is not particularly limited, but is preferably 0.50 or more, more preferably 0.70 or more, in terms of a molar ratio to 1 mol of the diols in total. More preferably 0.80 or more, still more preferably 0.90 or more, particularly preferably 0.95 or more, most preferably 0.98 or more, preferably 1.20 or less, more preferably 1.15 or less, 1.10 or less is more preferable. When the amount of carbonic acid diester used is less than the lower limit, polymerization may not proceed to a predetermined molecular weight. When the upper limit is exceeded, the proportion of the polycarbonate diol end group that is not a hydroxyl group increases, or the molecular weight is predetermined. In some cases, the polycarbonate diol used in the present invention cannot be produced.

  In the production of the polycarbonate diol used in the present invention, the ratio of the amount of raw material diol that gives structure (A) and the amount of raw material diol that gives structure (B) (hereinafter referred to as “raw material (A) / raw material (B) ratio”. Is usually a molar ratio of the raw material diol giving the structure (A) / the raw material diol giving the structure (B) = 99/1 to 1/99. By introducing the structure (B) into the molecular chain, the regularity of the polycarbonate diol is disturbed, so that the melting point and the viscosity are lowered and the handling property is improved. The above-mentioned effects such as rigidity and hydrophilicity are mainly caused by the structure (A). If the proportion of the structure (A) in the polycarbonate diol used in the present invention is too small, the effect cannot be sufficiently obtained. There is a case. The raw material (A) / raw material (B) ratio is preferably 99/1 to 10/90, more preferably 80/20 to 20/80, and still more preferably 70/30 to 30/70.

  In the production of the polycarbonate diol used in the present invention, when an ester exchange catalyst is used, the upper limit of the amount used is preferably an amount that does not affect the performance even if remaining in the obtained polycarbonate diol. The mass ratio in terms of metal to mass is preferably 500 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, and the lower limit is preferably an amount that provides sufficient polymerization activity, preferably 0.01 ppm or more, 0.1 ppm or more is more preferable, and 1 ppm or more is still more preferable.

{Reaction conditions, etc.}
The method for charging the reaction raw material is not particularly limited, and the entire amount of diol, carbonic acid ester and catalyst is charged at the same time, and the method is used for the reaction. A method of adding a diol and a catalyst later, a method of adding and melting a diol first, and adding a carbonate ester and a catalyst thereto, and reacting a part of the diol with a carbonate ester or a chloro carbonate ester. The method can be freely selected, for example, by synthesizing a diester carbonate derivative of a diol and then reacting with the remaining diol. In the polycarbonate diol used in the present invention, a method in which a part of the diol to be used is added at the end of the reaction in order to make the ratio of the number of molecular chain terminal alkyloxy group or aryloxy group within the above range is adopted. It is also possible to do. In this case, the amount of diol added at the end is usually 20% or less (preferably 15% or less, more preferably 10% or less) of the amount of diol to be charged, and usually 0.1% or more (preferably 0.5% or more, more preferably 1.0% or more).

  The reaction temperature in the transesterification reaction can be arbitrarily adopted as long as a practical reaction rate can be obtained. The temperature is not particularly limited, but is usually 70 ° C. or higher (preferably 100 ° C. or higher, more preferably 130 ° C. or higher), and usually 250 ° C. or lower (preferably 230 ° C. or lower, more preferably 200 ° C. or lower, The temperature is preferably 180 ° C. or less, particularly preferably 170 ° C. or less, and most preferably 165 ° C. or less. If the reaction temperature exceeds the upper limit, the resulting polycarbonate diol is colored, an ether structure is formed, or the terminal (A) ratio (I) becomes too large. When producing a cured product, quality problems such as insufficient expression of desired physical properties may occur.

  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 while distilling off the light boiling component by adopting a reduced pressure condition in the second half of the reaction. Or it is also possible to make it react, distilling off the light boiling component produced | generated by reducing pressure gradually from the middle of reaction. In particular, it is preferable to carry out the reaction by increasing the degree of vacuum at the end of the reaction, because by-produced monoalcohol, phenols, and cyclic carbonate can be distilled off. The reaction pressure at the end of the reaction is not particularly limited, but is usually 10 kPa or less (preferably 5 kPa or less, more preferably 1 kPa or less). In order to effectively distill these light-boiling components, the reaction can be carried out while passing a small amount of an inert gas such as nitrogen, argon or helium through the reaction system.

  When using low-boiling carbonates or diols in the transesterification reaction, the reaction is started near the boiling point of the carbonates or diols at the beginning of the reaction, and the temperature is gradually raised as the reaction proceeds to further react. It is also possible to adopt a method of proceeding. This is preferable because unreacted carbonate ester can be prevented from distilling off at the beginning of the reaction. Furthermore, it is also possible to attach the reflux tube to the reactor in order to prevent the raw materials from distilling off at the initial stage of the reaction, and perform the reaction while refluxing the carbonate ester and the diol. In this case, it is preferable because the charged raw materials are not lost and the amount ratio of the reagents can be accurately adjusted.

  The polymerization reaction is performed while measuring the molecular weight of the produced polycarbonate diol, and is terminated when the target molecular weight is reached. The reaction time required for the polymerization varies greatly depending on the diol, carbonate, catalyst used, and type used, and cannot be defined unconditionally. However, the reaction time required to reach a predetermined molecular weight is usually 50. Or less (preferably 20 hours or less, more preferably 10 hours or less).

  As described above, when a catalyst is used in the polymerization reaction, the catalyst is usually left in the polycarbonate diol obtained, and the remaining metal catalyst may make it impossible to control the reaction when performing the polyurethane reaction. is there. In order to suppress the influence of this residual catalyst, a substantially equimolar amount of, for example, a phosphorus compound may be added to the transesterification catalyst used. Furthermore, after the addition, the transesterification catalyst can be inactivated efficiently by heat treatment as described later. Examples of the phosphorus compound used for inactivating the transesterification catalyst include inorganic phosphoric acid such as phosphoric acid and phosphorous acid, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, And organic phosphate esters such as triphenyl phosphate. These may be used alone or in combination of two or more.

  The amount of the phosphorus compound used is not particularly limited, but as described above, it may be approximately equimolar with the transesterification catalyst used, and specifically, with respect to 1 mol of the transesterification catalyst used. 5 mol or less is preferable, 2 mol or less is more preferable, 0.8 mol or more is preferable, and 1.0 mol or more is more preferable. When the amount of the phosphorus compound used is less than the lower limit, the transesterification catalyst in the reaction product is not sufficiently deactivated, and the obtained polycarbonate diol is used, for example, as a raw material for producing a polyurethane (meth) acrylate oligomer. Sometimes, the reactivity of the polycarbonate diol with respect to the isocyanate group cannot be sufficiently lowered. Moreover, when the usage-amount of a phosphorus compound exceeds the said upper limit, the obtained polycarbonate diol may color.

  The inactivation of the transesterification catalyst by adding a phosphorus compound can be performed at room temperature, but it is more efficient when heated. The temperature of this heat treatment is not particularly limited, but is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, further preferably 100 ° C. or lower, more preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and 70 ° C. The above is more preferable. If the temperature of the heat treatment is less than the lower limit, it takes time to deactivate the transesterification catalyst, which is not efficient, and the degree of deactivation may be insufficient. On the other hand, when the temperature of the heat treatment exceeds the upper limit, 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.

{Purification}
After the reaction, the terminal structure in the polycarbonate diol product is an impurity having an alkyloxy group, an impurity having an aryloxy group, a phenol, a raw material diol or carbonate, a by-product light-boiling cyclic carbonate, and further added. Purification can be performed for the purpose of removing the 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. 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 dissolved in water can be selected arbitrarily.

(Polyisocyanate)
The polyisocyanate used in the present invention is a compound having one or both of two or more isocyanate groups and a substituent containing an isocyanate group (also referred to as “isocyanate groups”) in one molecule. Polyisocyanate may be used individually by 1 type, or may use 2 or more types together. Moreover, in 1 type of polyisocyanate, isocyanate groups may be the same and may differ.

  Examples of the substituent containing an isocyanate group include an alkyl group having 1 to 5 carbon atoms, an alkenyl group, or an alkoxyl group containing one or more isocyanate groups. As carbon number, such as the said alkyl group as a substituent containing an isocyanate group, 1-3 are more preferable.

  The number average molecular weight of the polyisocyanate is preferably 100 or more, more preferably 150 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. Moreover, 1,000 or less are preferable and 500 or less are more preferable. 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. Aliphatic polyisocyanates are preferred 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 a linear or branched alkylene group having 1 to 6 carbon atoms is preferable. Examples of such aliphatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and carboxyl groups of dimer acid. And aliphatic diisocyanates such as dimerisocyanate converted into an isocyanate group, and aliphatic triisocyanates such as tris (isocyanatohexyl) isocyanurate. Among these, hexamethylene diisocyanate is preferable.

  The polyisocyanate used in the present invention is 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 thing containing is preferable. 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 a cycloalkylene group having 3 to 6 carbon atoms is preferable. 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, isophorone diisocyanate, methylcyclohexane diisocyanate, and tris ( And triisocyanate having an alicyclic structure such as isocyanate isophorone) isocyanurate. Among these polyisocyanates having an alicyclic structure, the viewpoint of increasing the strength and adhesion of a cured product obtained by curing the active energy ray-curable polymer composition, and less coloring over time, transparency. Bis (isocyanate methyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate are preferred from the viewpoint that they can be suitably used for the required materials.

  An aromatic polyisocyanate is a compound having an aromatic structure and two or more isocyanate groups bonded thereto. Although it does not specifically limit as an aromatic structure in aromatic polyisocyanate, A C6-C13 bivalent aromatic group is preferable. Examples of such aromatic polyisocyanates include xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl -4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate and m-tetramethylxylylene Aromatic diisocyanates such as diisocyanate. Of these aromatic polyisocyanates, tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate are preferable from the viewpoint of increasing the mechanical strength of a cured product obtained by curing the active energy ray-curable polymer composition.

(Hydroxyalkyl (meth) acrylate)
The hydroxyalkyl (meth) acrylate used in the present invention is a compound having one or more hydroxyl groups, one or more (meth) acryloyl groups, and a hydrocarbon group having 1 to 30 carbon atoms. A hydroxyalkyl (meth) acrylate may be used individually by 1 type, or may use 2 or more types together.

  Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and cyclohexane di Addition reaction product of methanol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate and caprolactone, addition reaction product of 4-hydroxybutyl (meth) acrylate and caprolactone, addition of glycidyl ether and (meth) acrylic acid Examples include reactants, mono (meth) acrylates of glycol, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Among these, carbon number is 2-4 between (meth) acryloyl groups, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and a hydroxyl group. A hydroxyalkyl (meth) acrylate having an alkylene group is particularly preferred from the viewpoint of the mechanical strength of the resulting cured film. The molecular weight of the hydroxyalkyl (meth) acrylate is preferably 40 or more, more preferably 80 or more, and preferably 800 or less, more preferably 400 or less, from the viewpoint of the mechanical strength of the resulting cured film. In addition, when the said hydroxyalkyl (meth) acrylate is the said addition reactant or polymer, the said molecular weight is a number average molecular weight.

(Other ingredients)
The polyurethane (meth) acrylate oligomer used in the present invention may further contain other components in the raw material as long as the effects of the present invention are obtained. Examples of such other components include other polyols other than the polycarbonate diol containing the structure (A) and the structure (B), and a chain extender.

  Other polyols excluding the polycarbonate diol containing the structure (A) and the structure (B) are compounds having two or more hydroxyl groups (however, excluding the polycarbonate diol containing the structure (A) and the structure (B)) ). Such other polyols include high molecular weight polyols having a number average molecular weight exceeding 500, excluding the polycarbonate diol containing the structure (A) and the structure (B), the structure (A) and the structure (B). Examples thereof include low molecular weight polyols having a number average molecular weight of 500 or less excluding polycarbonate diol.

  Examples of the high molecular weight polyol having a number average molecular weight exceeding 500 include, for example, polyether diol, polyester diol, polyether ester diol, polycarbonate diol other than polycarbonate diol containing the structure (A) and the structure (B), Examples include polyolefin polyol and silicon polyol. Examples of the low molecular weight polyol having a number average molecular weight of 500 or less include aliphatic diols, alicyclic diols, and aromatic diols. Such high molecular weight polyols and low molecular weight polyols may be used alone or in combination of two or more.

  Examples of the polyether diol include compounds obtained by ring-opening polymerization of a cyclic ether, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Examples of the polyester diol include compounds obtained by polycondensation of a dicarboxylic acid or an anhydride thereof and a low molecular weight diol, such as polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, and polybutylene sebacate. Can be mentioned. 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. Examples of the dicarboxylic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and phthalic acid. Examples of dicarboxylic acid anhydrides 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, poly Tetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexaneglycol, 2,2,4- Trimethyl-1,3-pentanediol, 3, - dimethylol heptane, 1,9-nonanediol, 2-methyl-1,8-octanediol, cyclohexanedimethanol, and include 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. For example, poly (polytetramethylene ether) adipate includes Can be mentioned.

  Examples of the other polycarbonate diol include polybutylene carbonate, polyhexamethylene carbonate, poly (3-methyl-1,5-pentylene) obtained by deglycolization or dealcoholization from the low molecular weight diol and alkylene carbonate or dialkyl carbonate. ) Carbonate and the like and copolymers thereof.

  The polyolefin polyol is a polyolefin having two or more hydroxyl groups. The polyolefin polyol may be used alone or in combination of two or more. Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol.

  The silicon polyol is a silicone having two or more hydroxyl groups. The silicon polyol may be used alone or in combination of two or more. Examples of the silicon polyol include polydimethylsiloxane polyol.

  Among these high molecular weight polyols, the other polycarbonate diols are preferable from the viewpoints of weather resistance and mechanical strength of a cured product obtained by curing the active energy ray-curable polymer composition. The other polycarbonate diol has good workability without significantly increasing the viscosity of the polyurethane (meth) acrylate oligomer as the number average molecular weight decreases, and also cures the active energy ray-curable polymer composition. There is a tendency that the mechanical strength and stain resistance of the cured product obtained in this manner 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 still more preferably 2,000 or less.

  Examples of the aliphatic diol 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-di Ji roll heptane, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol and the like.

  Examples of the alicyclic diol include cyclopropanediol, cyclopropanedimethanol, cyclopropanediethanol, cyclopropanedipropanol, cyclopropanedibutanol, cyclopentanediol, cyclopentanedimethanol, cyclopentanediethanol, cyclopentanedipropanol, cyclopropane Pentanedibutanol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, cyclohexanedipropanol, cyclohexanedibutanol, cyclohexenediol, cyclohexenedimethanol, cyclohexenediethanol, cyclohexenedipropanol, cyclohexenedibutanol, cyclohexadienediol, cyclohexadienedimethanol, cyclohexane Hexadiene dietano Le, cyclohexadienyl engine propanol, cyclohexadienyl engine butanol, hydrogenated bisphenol A, tricyclodecane diol, adamantyl diol.

  Examples of the aromatic diol include bishydroxyethoxybenzene, bishydroxyethyl terephthalate, and bisphenol-A.

  Further, dialkanolamines such as N-methyldiethanolamine; pentaerythritol; sorbitol; mannitol; glycerin; trimethylolpropane and the like can also be used as other components.

  Among these low molecular weight polyols, aliphatic diols and alicyclic diols are preferable from the viewpoint of the weather resistance of the resulting cured film. In applications where the mechanical strength of the cured product is required, the low molecular weight polyol may be ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propane. Polyol 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, hydrogenated An alicyclic polyol in which two hydroxyl groups such as bisphenol A are present at symmetrical positions with an alicyclic structure in between is particularly preferable.

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

  The chain extender is a compound having two or more active hydrogens that react with isocyanate groups. A chain extender may be used individually by 1 type, or may use 2 or more types together. Examples of such chain extenders include low molecular weight diamine compounds having a number average molecular weight of 500 or less, 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 chloromethanemethanediamine (hydrogenated MDA), isopropylidenecyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, and tricyclodecanediamine. . Among these, 1,4-butanediol, 1,5-pentanediol, 1,6-butanediol are preferable from the viewpoint of preferable balance of physical properties of the obtained cured product and industrially available in large quantities at low cost. Hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, 1,3-aminopropane and the like are preferable.

{Molecular weight measurement method}
The molecular weight or number average molecular weight of the aforementioned raw material compound such as polycarbonate diol containing the structure (A) and the structure (B) is a compound other than a polyol having a molecular weight distribution in a gel permeation chromatogram (hereinafter abbreviated as GPC). As for, the molecular weight can be calculated from the chemical formula, or the number average molecular weight can be determined by GPC. Moreover, about the polyol which has molecular weight distribution in GPC, the number average molecular weight can be calculated | required by OH value.

{Calculation of number average molecular weight by GPC}
Using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation), tetrahydrofuran as a solvent, polystyrene as a standard sample, TSK gel superH1000 + H2000 + H3000 as a column, liquid feeding speed 0.5 cm ³ / min, column oven temperature 40 ° C. The number average molecular weight is measured.

{Calculation of polyisocyanate number average molecular weight by NCO%}
In 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 in the same manner as described above except that the polyisocyanate is not added to the Erlenmeyer flask to obtain a blank. 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 aqueous hydrochloric acid solution required for titration of blank solution containing no polyisocyanate (ml)
Number average molecular weight of polyisocyanate = (42.02 / NCO%) × number of NCO groups.

  In the above formula, the “number of NCO groups” is the number of NCO groups contained in one molecule of polyisocyanate.

{Calculation of number average molecular weight of polyol by OH number}
Into an Erlenmeyer flask, 2 g of polyol and 0.5 mol / liter of a phthalic anhydride pyridine solution are allowed to react at 100 ° C. for 2 hours, and then diluted with 150 mL of acetone. Thereafter, it is titrated with a 0.5 mol / liter sodium hydroxide aqueous solution. Moreover, titration is performed in the same manner as described above 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 = {(B2-A2) × 0.5 × 56.11 × 1000} / (2 × 1000)
A2: Amount of sodium hydroxide aqueous solution required for titration of polyol-containing solution (ml)
B2: Amount of sodium hydroxide aqueous solution required for titration of blank solution containing no polyol (ml)
Number average molecular weight of polyol = {(56.11 × 1000) / OH number} × number of functional groups In the above formula, “number of functional groups” means the number of OH groups contained in one molecule of polyol. It is.

(Polyurethane (meth) acrylate oligomer)
In the polyurethane (meth) acrylate oligomer used in the present invention, the amount of all isocyanate groups and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually equimolar, and in mol%. expressed.

  That is, the use amount of the polyisocyanate, polycarbonate diol, hydroxyalkyl (meth) acrylate, and other raw material compounds in the polyurethane (meth) acrylate oligomer is the amount of all isocyanate groups in the polyurethane (meth) acrylate oligomer and that. The amount of all functional groups to be reacted is an equivalent mole or 50 to 200 mol% in terms of mol% of functional groups with respect to isocyanate groups.

  When producing polyurethane (meth) acrylate oligomers, the amount of hydroxyalkyl (meth) acrylate used is hydroxyalkyl (meth) acrylate, polycarbonate diol, high molecular weight polyol, low molecular weight polyol, chain extender, etc. Is usually 10 mol% or more (preferably 15 mol% or more, more preferably 25 mol% or more), and usually 70 mol% or less (preferably, based on the total amount of the compound containing a functional group that reacts with isocyanate. 50 mol% or less). According to this ratio, the molecular weight of the obtained polyurethane (meth) acrylate oligomer can be controlled. As the proportion of hydroxyalkyl (meth) acrylate increases, the molecular weight of the polyurethane (meth) acrylate oligomer tends to decrease, and as the proportion decreases, the molecular weight tends to increase.

  The use amount of the polycarbonate diol with respect to the total use amount of the polycarbonate diol and the high molecular weight polyol is preferably 25 mol% or more, and preferably 50 mol% or more, from the viewpoint that the hardness and stain resistance of the cured product are improved. Is more preferable, and 70 mol% or more is still more preferable.

  The amount of the polycarbonate diol used relative to the total amount of the polycarbonate diol, the high molecular weight polyol and the low molecular weight polyol is 25 mol% or more from the viewpoint of improving the elongation and weather resistance of the cured product. Preferably, 50 mol% or more is more preferable, and 70 mol% or more is still more preferable.

  Further, in the case where the polyurethane (meth) acrylate oligomer is a reaction product containing a chain extender, the total of the polycarbonate diol, the high molecular weight polyol, and the total compound of the low molecular weight polyol and the chain extender are combined. The amount of all polyols used relative to the amount used is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 95 mol% or more from the viewpoint of improving liquid stability. preferable.

{Production method of polyurethane (meth) acrylate oligomer}
The polyurethane (meth) acrylate oligomer used in the present invention is produced by adding the polycarbonate diol containing the structure (A) and the structure (B) and the hydroxyalkyl (meth) acrylate to the polyisocyanate. can do. Here, when the other polyol and the chain extender are used together as raw materials, the polyurethane (meth) acrylate oligomer used in the present invention is added to the polyisocyanate in addition to the other raw material compounds described above. Can be produced by addition reaction. These addition reactions can be performed by any known method. Examples of such a method include the following methods (1) to (3).
(1) After obtaining an isocyanate-terminated urethane prepolymer obtained by reacting components other than the hydroxyalkyl (meth) acrylate under conditions such that the isocyanate group becomes excessive, the isocyanate-terminated urethane prepolymer and the hydroxyalkyl ( A prepolymer method in which a (meth) acrylate is reacted.
(2) One-shot method in which all components are added simultaneously and reacted.
(3) obtained after 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 other pre-polymer components with the prepolymer.

  Among these, according to the method (1), the urethane prepolymer is obtained by urethanating the polyisocyanate and the polycarbonate diol, and the polyurethane (meth) acrylate oligomer has an isocyanate group at the terminal. Since it has a structure obtained by urethanation reaction of urethane prepolymer and hydroxyalkyl (meth) acrylate, the molecular weight can be controlled and acryloyl groups can be introduced at both ends. From such a viewpoint, the method (1) is preferable.

  In the production of the polyurethane (meth) acrylate oligomer, a solvent can be used for the purpose of adjusting the viscosity. A solvent may be used individually by 1 type, or may use 2 or more types together, In the range in which the effect of this invention is acquired, all the well-known solvents can be used. Examples of such solvents include aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, nonane, octane, isooctane, and decane; aromatic carbonized solvents such as benzene, toluene, xylene, cumene, and ethylbenzene. Hydrogen; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as diethyl ether, diisopropyl ether and methyl tert-butyl ether; ketones such as cyclohexanone, methyl ethyl ketone, dimethyl ketone, diethyl ketone, diisopropyl ketone and methyl isobutyl ketone A solvent is mentioned. Of these solvents, toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone are preferred. A solvent can be normally used in less than 300 mass parts with respect to 100 mass parts of active energy ray-curable polymer compositions.

  At the time of production of the polyurethane (meth) acrylate oligomer, the total content of the polyurethane (meth) acrylate oligomer and its raw material is 20 with respect to the total amount from the viewpoint of increasing the reaction rate and improving the production efficiency. % By mass or more is preferable, and 40% by mass or more is more preferable. In addition, the upper limit of this total content is 100 mass%.

  In the production of the polyurethane (meth) acrylate oligomer, the reaction temperature is usually 20 ° C. or higher (preferably 40 ° C. or higher, more preferably 60 ° C. or higher) from the viewpoint of increasing the reaction rate and improving the production efficiency. is there. Further, from the viewpoint that side reactions such as allohanato reaction hardly occur, the reaction temperature is usually 120 ° C. or lower (preferably 100 ° C. or lower). Moreover, when the solvent is contained in the reaction liquid, the boiling point or lower of the solvent is preferable, and when (meth) acrylate is contained, 70 ° C. or lower is preferable from the viewpoint of preventing the reaction of the (meth) acryloyl group. The reaction time is usually about 5 to 20 hours.

  The addition reaction catalyst in the production of the polyurethane (meth) acrylate oligomer can be selected from the range in which the effects of the present invention can be obtained. For example, dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, dioctyltin dioctoate Bismuth tris (2-ethylhexanoate), diisopropoxytitanium bis (acetylacetonate), titanium tetra (acetylacetonate), dioctanoxytitanium dioctanoate, diisopropoxytitanium bis (ethylacetoacetate), etc. The well-known urethane polymerization catalyst represented is mentioned. An addition reaction catalyst may be used individually by 1 type, or may use 2 or more types together. Of these addition reaction catalysts, bismuth tris (2-ethylhexanoate) is preferable from the viewpoints of environmental adaptability, catalytic activity, and storage stability.

  When the reaction liquid contains a (meth) acryloyl group during the production of the polyurethane (meth) acrylate oligomer, 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. , Copper salts such as copper, manganese salts such as manganese acetate, nitro compounds, and nitroso compounds. A polymerization inhibitor may be used individually by 1 type, or may use 2 or more types together. Of these polymerization inhibitors, phenols are preferred.

  Moreover, the preparation ratio of each raw material component is substantially the same (preferably the same) as the composition of the polyurethane (meth) acrylate oligomer used in the present invention.

[Active energy ray reactive monomer]
In the present invention, active energy rays are used for the purpose of adjusting the hydrophilicity / hydrophobicity of the polyurethane (meth) acrylate oligomer and the physical properties such as hardness and elongation of the cured product when the resulting composition is cured. Use reactive monomers. Examples of such active energy ray reactive monomers include aromatic vinyl monomers, vinyl ester monomers, vinyl ethers, allyl compounds, (meth) acrylamides, and (meth) acrylates. For example, aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene; vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl Vinyl ester monomers such as 2-pyrrolidone, N-vinylcaprolactam, and divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; and esters such as diallyl phthalate, trimethylolpropane diallyl ether, and allyl glycidyl ether Ryl compounds; acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt-butylacrylamide, acryloylmorpholine, methylenebis (Meth) acrylamides such as 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, (meth) Tetrahydrofurfuryl acrylate (Meth) acrylic acid morpholyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid glycidyl, (meth) Dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, (meth) acrylic acid Dicyclopentenyl, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, isobornyl (meth) acrylate, Monofunctional such as phenyl (meth) acrylate Meth) acrylate; and ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene di (meth) acrylate Glycol (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) acrylic acid polypropylene glycol (n = 5 to 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) Poly (1-methylbutylene glycol) acrylate (n = 5 to 20), di (meth) acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonanediol, di (meth) Neopentyl glycol acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, dicyclopentanediol di (meth) acrylate, tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaeryth Tall hexa (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 building phenol F di (meta) ) Acrylate, propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acryl Chromatography, tri tricyclodecane dimethanol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, polyfunctional (meth) acrylates such as bisphenol F epoxy di (meth) acrylate. These active energy ray reactive monomers may be used alone or in combination of two or more.

  Among these, in particular, in applications where coating properties are required for the active energy ray-curable polymer composition of the present invention, (meth) acryloylmorpholine, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid benzyl, (Meth) acrylic acid cyclohexyl, (meth) acrylic acid trimethylcyclohexyl, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid tricyclodecane, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid isobornyl, mono ( Monofunctional (meth) acrylates having a ring structure in the molecule, such as (meth) acrylamide, are preferable, while di (meth) acrylic acid-1,4-butane is used in applications where mechanical strength of the resulting cured product is required. Diol, di (meth) acrylic acid-1,6-hexanediol, di (meth) Crylic acid-1,9-nonanediol, neopentyl glycol di (meth) acrylate, tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Polyfunctional (meth) acrylates such as (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

(Active energy ray-curable polymer composition)
In the active energy ray-curable polymer composition of the present invention, the blending amount of the polyurethane (meth) acrylate oligomer is 1% by mass or more and 45% by mass or less with respect to 100% by mass of the composition. From the viewpoint of adjusting the viscosity and adjusting physical properties such as hardness and elongation of the cured product, it is preferably 5% by mass or more and 45% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and more preferably 15% by mass. More preferably, it is 30 mass% or less. Moreover, the compounding amount of the active energy ray-reactive monomer is 55% by mass or more and 99% by mass or less with respect to 100% by mass of the composition, and physical properties such as viscosity adjustment of the composition and hardness and elongation of the cured product. From the viewpoint of adjustment, it is preferably 55% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 90% by mass or less, and further preferably 70% by mass or more and 85% by mass or less.

(Method for producing active energy ray-curable polymer composition)
The active energy ray-curable polymer composition of the present invention can be produced by blending the polyurethane (meth) acrylate oligomer and the active energy ray-reactive monomer. The polyurethane (meth) acrylate oligomer can be produced by the methods (1) to (3) as described above.

Moreover, the active energy ray-curable polymer composition of the present invention is obtained by adding the polycarbonate diol and the hydroxyalkyl (meth) acrylate to the polyisocyanate in the presence of the active energy ray-reactive monomer. It can also be manufactured. Examples of such a method include the following methods (4) to (6).
(4) After obtaining an isocyanate-terminated urethane prepolymer obtained by reacting components other than the hydroxyalkyl (meth) acrylate in the presence of an active energy ray-reactive monomer under conditions such that the isocyanate group becomes excessive, A prepolymer method in which this isocyanate-terminated urethane prepolymer is reacted with the hydroxyalkyl (meth) acrylate.
(5) A one-shot method in which all components are simultaneously added and reacted in the presence of an active energy ray-reactive monomer.
(6) A urethane (meta) having a (meth) acryloyl group and an isocyanate group simultaneously in the molecule by reacting the polyisocyanate with the hydroxyalkyl (meth) acrylate in the presence of an active energy ray-reactive monomer. ) After synthesizing the acrylate prepolymer, the obtained prepolymer is reacted with other raw material components.

  In the methods (4) to (6), it is preferable that the active energy ray-reactive monomer does not have a functional group capable of reacting with an isocyanate group.

  Among these, according to the method (4), the urethane prepolymer is obtained by urethanating the polyisocyanate and the polycarbonate diol, and the polyurethane (meth) acrylate oligomer has an isocyanate group at the terminal. Since it has a structure obtained by urethanation reaction of urethane prepolymer and hydroxyalkyl (meth) acrylate, the molecular weight can be controlled and acryloyl groups can be introduced at both ends. From such a viewpoint, the method (4) is preferable.

  Therefore, the active energy ray-curable polymer composition of the present invention is produced by blending the urethane (meth) acrylate oligomer produced by the method (1) and the active energy ray-reactive monomer, or In the presence of an active energy ray-reactive monomer that does not have a functional group capable of reacting with an isocyanate group, it is preferably produced by the method (4).

  The active energy ray-curable polymer composition of the present invention further contains other components other than the polyurethane (meth) acrylate oligomer and the active energy ray-reactive monomer as long as the effects of the present invention are obtained. Also good. Examples of such other components include 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 polyurethane (meth) acrylate oligomer and the active energy ray-reactive monomer is excellent in curability and mechanical strength when used as a cured product. From the viewpoint of improving the three-dimensional processability without being too high, the total amount of active energy ray reactive components including the polyurethane (meth) acrylate oligomer and the active energy ray reactive monomer is 100% by mass. 40 mass% or more is preferable, and 60 mass% or more is more preferable. In addition, the upper limit of this content is 100 mass%.

  Further, in the active energy ray-curable polymer composition of the present invention, the content of the polyurethane (meth) acrylate oligomer and the active energy ray-reactive monomer is preferably larger in terms of elongation and film-forming property, On the other hand, less is preferable in terms of lowering the viscosity. From such a viewpoint, the content of the polyurethane (meth) acrylate oligomer and the active energy ray-reactive monomer is 100% by mass in total of all components including other components in addition to the active energy ray-reactive component. On the other hand, 50 mass% or more is preferable and 70 mass% or more is more preferable. In addition, the upper limit of this content is 100 mass% (preferably less than that).

  In the active energy ray-curable polymer composition of the present invention, the total content of the active energy ray-reactive component including the polyurethane (meth) acrylate oligomer and the active energy ray-reactive monomer is 60% by mass or more is preferable, 80% by mass or more is more preferable, and 90% by mass or more is preferable with respect to 100% by mass of the composition in terms of excellent curing speed and surface curability as a product and no tack remains. More preferred is 95% by mass or more. In addition, the upper limit of this content is 100 mass%.

  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 an epoxy (meth) acrylate oligomer, an acrylic (meth) acrylate oligomer, an ester (meth) acrylate oligomer, an ether (meth) acrylate oligomer, the structure (A), and the structure. Polyurethane which is a reaction product of a raw material containing at least one polyol selected from the group consisting of polycarbonate polyols other than polycarbonate diol containing (B), ester polyols and ether polyols, polyisocyanate and hydroxyalkyl (meth) acrylate (Meth) acrylate oligomers may be mentioned. Such an active energy ray-curable oligomer can be blended to such an extent that it does not affect physical properties such as hardness and elongation of the resulting cured product.

  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 such an active energy ray 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 within a range in which the effect of the present invention can be obtained. A polymerization initiator can also be used. A polymerization initiator may be used individually by 1 type, or may use 2 or more types together. 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.

  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 preferred.

  In addition, when the active energy ray-curable polymer composition of the present invention includes a compound having a radical polymerizable group and a cationic polymerizable group such as an epoxy group, the above-mentioned photo radical polymerization initiator is used as a polymerization initiator. In addition, a photocationic 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 photopolymerization initiators in the active energy ray-curable polymer composition of the present invention is the active energy ray-reactive component described above from the viewpoint that mechanical strength is not easily lowered by the initiator decomposition product. Is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass in total.

  The photosensitizer can be used for the same purpose as the polymerization initiator. A photosensitizer may be used individually by 1 type, or may use 2 or more types together. 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, as the content of the photosensitizer, the active energy ray-reactive component of the active energy ray-reactive component is preferably used from the viewpoint that mechanical strength is not easily lowered due to a reduction in crosslinking density. 10 mass parts or less are preferable with respect to a total of 100 mass parts, and 5 mass parts or less are more preferable.

  As the additive, various materials added to the composition used for the same application can be used as the additive as long as the effects of the present invention are obtained. An additive may be used individually by 1 type, or may use 2 or more types together. 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, anti-fingerprint agent, surface hydrophilizing agent, antistatic agent, slipperiness imparting agent, plasticizer, mold release agent, antifoaming agent, leveling agent, anti-settling agent, surface activity Agents, thixotropy imparting agents, lubricants, flame retardants, flame retardant aids, polymerization inhibitors, fillers, silane coupling agents and other modifiers; pigments, dyes, color modifiers such as hue modifiers; and monomers And / or oligomer thereof, or a curing agent required for the synthesis of inorganic components, catalysts include curing accelerators and the like.

  In the active energy ray-curable polymer composition of the present invention, the content of the additive is a total of 100 of the active energy ray-reactive components from the viewpoint that the mechanical strength is not easily lowered due to the reduced crosslinking density. 10 parts by mass or less is preferable and 5 parts by mass or less is more preferable with respect to parts by mass.

  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, or may use 2 or more types together, In the range in which the effect of this invention is acquired, all the well-known solvents can be used. As such a solvent, toluene, xylene, ethyl acetate, butyl acetate, isopropanol, isobutanol, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone are preferable. A solvent can be normally used in less than 400 mass parts with respect to 100 mass parts of active energy ray-curable polymer compositions.

  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 it is 25 ° C. in an E-type viscometer (rotor 1 ° 34 ′ × R24). The viscosity is preferably 10 mPa · s or more, more preferably 100 mPa · s or more, and more preferably 100,000 mPa · s from the viewpoints of handleability, coatability, moldability, three-dimensional formability, and the like. s or less is preferable, and 50,000 mPa · s or less is more preferable. The adjustment of the viscosity of the active energy ray-curable polymer composition is adjusted by, for example, the content of the polyurethane (meth) acrylate oligomer and the active energy ray-reactive monomer, the kind of the optional component, the blending ratio thereof, and the like. be able to.

  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 cured film of the present invention can be obtained by irradiating the coating film made of the active energy ray-curable polymer composition of the present invention with active energy rays. Examples of active energy rays used for curing the composition include infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, and the like. From the viewpoint of equipment cost and productivity, it is preferable to use an electron beam or ultraviolet light, and as a light source, an electron beam irradiation device, 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 laser, He—Cd laser, solid laser, xenon lamp, high frequency induction mercury lamp, sunlight, etc. 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 by electron beam irradiation, the irradiation amount is preferably 1 to 10 Mrad. In the case of ultraviolet irradiation, 50 to 1,000 mJ / cm ² is preferable. 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 film thickness of the cured film of the present invention is appropriately determined according to the intended use, but is preferably 1 μm or more, more preferably 3 μm or more, particularly preferably 5 μm or more, and preferably 200 μm or less, 100 μm. The following is more preferable, 50 μm or less is particularly preferable, and 20 μm or less is most preferable. When the film thickness is equal to or greater than the lower limit, the design properties and functionality after three-dimensional processing are improved, and when the film thickness is equal to or less than the upper limit, internal curability and suitability for three-dimensional processing are favorable.

  Moreover, the laminated body of this invention is equipped with the layer which consists of such a cured film of this invention. For example, the laminated body which has a layer which consists of a base material and the cured film of this invention arrange | positioned on this base material is mentioned. In the laminate of the present invention, a layer other than the substrate and the cured film of the present invention may be disposed between the substrate and the layer comprising the cured film of the present invention. Layers other than the base material and the cured film of the present invention may be disposed outside the laminate with the layer made of the cured film. Moreover, the laminated body of this invention may have multiple layers which consist of a base material and the cured film of this invention.

  As a method for producing the laminate of the present invention, all layers are laminated in an uncured state and then cured with active energy rays, and the lower layer is cured or semi-cured with active energy rays and then the upper layer is applied again. A known method such as a method of curing with active energy rays, a method of laminating layers in an uncured or semi-cured state after applying each layer to a release film or a base film can be applied. From the viewpoint of improving the adhesiveness, a method of curing with an active energy ray after laminating in an uncured state 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 kinds of polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polypropylene and polyester, various plastics such as nylon, polycarbonate, and (meth) acrylic resin, and plates made of metal. Shaped articles can be mentioned.

  Since the cured film of the present invention is high in hardness and has good scratch resistance, but has good flexibility, the laminate of the present invention used as a film on various substrates has a design property and Excellent surface protection.

  In addition, in the active energy ray-curable polymer composition of the present invention, a cured film having an excellent balance between suitability for three-dimensional processing and contamination resistance can be obtained in consideration of the molecular weight between calculated network crosslinking points. For example, from the viewpoint that the three-dimensional workability of the obtained cured film becomes good and the balance between the three-dimensional workability and the stain resistance is excellent, the calculated energy-crosslinking point of the active energy ray-curable polymer composition of the present invention is between The molecular weight is preferably 500 or more, more preferably 800 or more, and still more preferably 1,000 or more. In addition, the molecular weight between the calculated network cross-linking points is preferably 10,000 or less from the viewpoint that the obtained cured film has good stain resistance and an excellent balance between suitability for three-dimensional processing and stain resistance. 000 or less is more preferable, 6,000 or less is more preferable, 4,000 or less is particularly preferable, and 3,000 or less is most 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.

  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 active energy rays. A network structure is formed when a compound having two or more 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 kind of polyfunctional compound reacts, the molecular weight between calculated network crosslinking 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.

{Usage}
The active energy ray-curable polymer composition of the present invention can express various properties and is widely used in elastomers, paints, fibers, adhesives, flooring materials, sealants, medical materials, artificial leather, coating agents, and the like. Can be used. In particular, when the active energy ray-curable polymer composition of the present invention is used for artificial leather, synthetic leather, adhesives, medical materials, flooring materials, coating agents, etc., it is excellent in friction resistance and blocking resistance. Therefore, it is possible to impart good surface characteristics such that scratches due to scratching and the like are difficult to be caused and deterioration due to friction is small.

  Moreover, the active energy ray-curable polymer composition of the present invention can also be applied for use as a thermoplastic elastomer. For example, it can be used for tubes and hoses, spiral tubes, fire hoses, etc. in pneumatic equipment, coating equipment, analytical equipment, physics and chemistry equipment, metering pumps, water treatment equipment, industrial robots and the like used in the food and medical fields. Moreover, it is used for various power transmission mechanisms, spinning machines, packing equipment, printing machines and the like as belts such as round belts, V belts, and flat belts. Also, it can be used for footwear heel tops, shoe soles, couplings, packings, pole joints, bushes, gears, rolls and other equipment parts, sports equipment, leisure goods, watch belts, and the like. Furthermore, examples of automobile parts include oil stoppers, gear boxes, spacers, chassis parts, interior parts, tire chain substitutes, and the like. In addition, it can be used for films such as keyboard films and automobile films, curl cords, cable sheaths, bellows, transport belts, flexible containers, binders, synthetic leather, depinning products, adhesives, and the like.

  The active energy ray-curable polymer composition of the present invention can be applied to wood products such as musical instruments, Buddhist altars, furniture, decorative plywood, and sports equipment. It can also be used for automobile repair.

  The active energy ray-curable polymer composition of the present invention includes, for example, a plastic bumper coating, a strippable paint, a magnetic tape coating agent, a floor tile, a flooring material, paper, an overprint varnish such as a wood grain printing film, It can be applied to wood varnishes, high processing coil coats, optical fiber protective coatings, solder resists, metal printing top coats, vapor deposition base coats, food can white coats, and the like.

  The active energy ray-curable polymer composition of the present invention can be applied as an adhesive to food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, OCR materials inside liquid crystal panels, and the like.

  In addition, the active energy ray-curable polymer composition of the present invention includes metal materials such as iron, copper, aluminum, ferrite, and plated steel, acrylic resin, polyester resin, ABS resin, polyamide resin, polycarbonate resin, vinyl chloride resin, and the like. Inorganic materials such as resin materials, glass and ceramics can be efficiently bonded.

  The active energy ray-curable polymer composition of the present invention includes, as a binder, a magnetic recording medium, ink, casting, fired brick, graft material, microcapsule, granular fertilizer, granular agricultural chemical, polymer cement mortar, resin mortar, rubber chip binder, It can be used for recycled foam and glass fiber sizing.

  The active energy ray-curable polymer composition of the present invention can be used as a component of a fiber processing agent for shrink-proofing, anti-molding, water-repellent processing, and the like.

  The active energy ray-curable polymer composition of the present invention is a concrete wall, induction joint, sash area, wall-type PC joint, ALC joint, board joint, composite glass sealant, heat insulating sash sealant as sealant caulking. Can be used for automobile sealant.

  Further, the active energy ray-curable polymer composition of the present invention can be used as a medical material, and as a blood compatible material, a tube, a catheter, an artificial heart, an artificial blood vessel, an artificial valve, etc., or a disposable material Can be used for catheters, tubes, bags, surgical gloves, artificial kidney potting materials, and the like.

  The active energy ray-curable polymer composition of the present invention is used as a raw material for UV curable paints, electron beam curable paints, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating materials, and the like. be able to.

  Among these, the active energy ray-curable polymer composition, the cured film and the laminate of the present invention are preferably used as a coating agent for a flexible material such as a foldable film. For example, a mobile phone, a monitor, a tablet It can be effectively applied to electronic devices such as touch panels and optical devices such as eyeglass lenses.

  When the active energy ray-curable polymer composition of the present invention is cured to give a cured film, it can give a cured film having excellent hardness, and the cured film can be used as a coating on various substrates. Surface protection can be imparted.

  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 one-layer coating.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In the following examples and comparative examples, “%” indicates “mass%” unless otherwise specified. Moreover, the measuring method of each physical property is shown below.

[Physical properties of polycarbonate diol]
<Hydroxyl value and number average molecular weight>
A phthalating agent was prepared by dissolving 14 g of phthalic anhydride in 100 ml of pyridine. In 5 ml of this phthalating agent, 1.50 to 1.60 g of polycarbonate diol was dissolved and reacted at 100 ° C. for 1 hour. The reaction mixture was cooled to room temperature and diluted with 25 ml of a THF / H ₂ O (75/25) mixed solvent. This solution was titrated with a 1N aqueous sodium hydroxide solution to determine the amount of the aqueous sodium hydroxide solution used until the inflection point was detected (this test). The same titration (blank test) was performed on a solution obtained by diluting 5 ml of a phthalating agent with 25 mL of a THF / H ₂ O (75/25) mixed solvent.

From the volume of the obtained sodium hydroxide aqueous solution, the hydroxyl value was determined by the following formula.
Hydroxyl value (mg-KOH / g) = {56.1 × (BA) × f} / S
A: Amount of 1N sodium hydroxide aqueous solution required for titration in this test (ml)
B: Amount of 1N aqueous sodium hydroxide solution required for titration in the blank test (ml)
f: titer of 1N aqueous sodium hydroxide solution S: sample (g)
Further, the number average molecular weight was calculated from the obtained hydroxyl value by the following formula.
Number average molecular weight of diol = {(56.1 × 1000) / OH number} × number of functional groups In the above formula, “number of functional groups” means the number of OH groups contained in one molecule of polyol. It is.

<(A) / (B) Ratio / Terminal (A) / (B) Ratio / Terminal (A) Rate (I)>
The product was dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (AVANCE400 manufactured by BRUKER) was measured and calculated from the integrated value. A specific calculation method is described below. That is, each ratio was calculated | required from the integrated value of the following chemical shift on an NMR chart. Note that the chemical shift value may vary slightly depending on the composition. In this case, the method of taking the integral value may be changed as appropriate.
Integral value of δ 5.22 to 4.98 ppm = a
Integral value of δ 4.79 to 4.61 ppm = b
Integral value of δ 4.61 to 4.47 ppm = c
Integral value of δ 3.68 to 3.51 ppm = d
Integral value of δ 2.73-2.66 ppm = e
Integral value of δ1.52-1.30 ppm = f
The structure (A) at the end of the molecular chain is two isomers, which are referred to as “(A) terminal 1” and “(A) terminal 2”, respectively. Further, the (A) -derived structural portion in the polycarbonate diol other than the terminal is referred to as “in (A)”. Similarly, regarding (B), “(B) end” and “(B) medium” are used. Considering the number of each proton, each number was calculated by the following formula.
(A) Terminal 1 = be
(A) Middle = c- (A) Terminal 1
(A) Terminal 2 = a- (A) Terminal 1- (A) × 2
(B) Terminal = (d-e- (A) Terminal 1) / 2
(B) Medium = (f− (B) terminal × 4) ÷ 4
The number of each structural formula in the molecular chain described in the formula (I) is expressed as follows.
Number of molecular chain terminal structures (A) = (A) terminal 1+ (A) terminal 2
Total number of structures (A) and structures (B) at molecular chain ends = (A) terminal 1+ (A) terminal 2+ (B) number of structures (A) in terminal molecular chain = (A) terminal 1+ (A ) Terminal 2+ (A) Total number of structures (A) and structures (B) in the molecular chain = (A) Terminal 1 + (A) Terminal 2+ (A) + (B) Terminal + (B) Above By applying the value to formula (I), the terminal (A) rate (I) was determined.

<Terminal phenoxide amount, ether bond amount, raw material diol amount, phenol amount>
The product was dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (AVANCE400 manufactured by BRUKER) was measured, and the product was calculated from the integrated value of the signal of each component. In this case, the detection limit is 200 ppm as the mass of terminal phenoxide with respect to the mass of the entire sample, 500 ppm as the mass of the ether group, 100 ppm as the mass of the raw material diol or phenol, 0.1 ppm by mass as isosorbide, o-dichlorobenzene As 200 ppm. Further, the ratio of terminal phenoxide is 1 of the integral value of one proton of terminal phenoxide and the entire terminal (total of the three structures of molecular chain terminal structure (A), molecular chain terminal structure (B), and terminal phenoxide). The detection limit of the terminal phenoxide is 0.05% with respect to the whole terminal.

<Residual amount of carbonate diester>
The residual amount of carbonic acid diester (diphenyl carbonate) was measured by GPC quantitative analysis under the following conditions.
(Analysis conditions)
Column: Tskel G2000H XL 7.8 mmI. D x 30 cmL 4 eluents: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
RI detector: RID-10A (Shimadzu Corporation).

<Average number of hydroxyl groups per molecule>
It was calculated by the following formula.
Average number of hydroxyl groups per molecule = [(number average molecular weight) × (hydroxyl value)] / [1000 × (KOH molecular weight)]
As the number average molecular weight value measured at ^{1 H-NMR} of the following, as the hydroxyl value was used to calculate values in the above titration.

<Number average molecular weight>
The number average molecular weight (Mn) was calculated from the integral value obtained by dissolving the product in CDCl ₃ and measuring ¹ H-NMR (AVANCE400 manufactured by BRUKER) at 400 MHz.

<Molecular weight distribution Mw / Mn>
The molecular weight distribution was calculated by obtaining polystyrene-converted Mn and Mw values by GPC measurement under the following conditions.
Apparatus: Tosoh 8020 manufactured by Tosoh Corporation
Column: PLgel 3um MIXED-E (7.5 mm ID × 30 cmL
× 2)
Eluent: THF (tetrahydrofuran)
Flow rate: 0.5 mL / min
Column temperature: 40 ° C
RI detector: RI (built in device Tosoh 8020).

<Viscosity>
The product was heated to 50 ° C., and then measured using an E-type viscometer (BROOKFIELD DV-II + Pro, corn: CPE-52).

[Physical properties of polyurethane (meth) acrylate oligomer]
<Remaining NCO>
0.2 g of the composition during the reaction was collected in an Erlenmeyer flask, and 10 ml of 0.1N dibutylamine was added and dissolved. Next, several drops of bromophenol blue solution were added, titrated with 0.1N hydrochloric acid ethanol solution, and the remaining NCO% was determined by the following formula.
NCO% = (a−b) × 0.42 × f / x
a: Titration amount of 0.1N hydrochloric acid ethanol solution when titrating the composition before reaction b: Titration amount of 0.1N hydrochloric acid ethanol solution when titrating the composition during reaction f: 0.1N hydrochloric acid ethanol solution Factor x: Sampling amount.

<Number average molecular weight>
The polyurethane (meth) acrylate-based oligomer contains three types of components, polyisocyanate, polycarbonate diol, and hydroxyalkyl (meth) acrylate as structural units. Since these structural units are formed while maintaining the molecular weight of each component in the urethane (meth) acrylate oligomer, in the following Examples and Comparative Examples, a polyurethane (meth) acrylate oligomer is generated. The average molecular weight of the polyurethane (meth) acrylate oligomer was calculated by the sum of the products of the molar ratios of the respective components and the molecular weight of the respective components.

<Molecular weight between calculation network cross-linking points>
The molecular weight between the calculated network cross-linking points is that the reactive group for the hydroxyalkyl (meth) acrylate in the polyurethane (meth) acrylate oligomer prepolymer is an isocyanate group at both ends of the prepolymer and is bonded to both ends of the prepolymer with urethane bonds. Since the hydroxyalkyl (meth) acrylate is added by radical polymerization, the crosslinking points of the urethane acrylate oligomer in the composition are (meth) acryloyl groups located at both ends of the polyurethane (meth) acrylate oligomer, and thus Since the obtained active energy ray-curable polymer composition becomes the bifunctional (polyfunctional) compound single system composition described above, it was determined from the following formula.

[Characteristics of cured film]
<Tensile breaking elongation, tensile breaking strength, tensile modulus>
The obtained cured film A was cut into a width of 1 cm, and using a desktop tensile strength tester (model number: Autograph AG-IS, manufactured by Shimadzu Corporation), the temperature was 20 ° C., the humidity was 60%, the tensile speed was 20 mm / min. A tensile test was performed under the condition of a distance between chucks of 50 mm, and the tensile elongation at break, tensile strength at break, and tensile elastic modulus of the cured film were measured.

  In addition, it means that it is a cured film which has elongation and favorable followable | trackability to a base material, so that tensile elongation at break is large. Moreover, it means that it is a cured film which is hard to break, so that tensile fracture strength is large. Furthermore, it means that it is a cured film which is hard to deform, so that a tensile elasticity modulus is large.

<Film forming properties>
The surface of the obtained cured film A was visually observed and evaluated according to the following criteria.
A: The cured film has no cracks and no cracks.
B: There is no crack in the cured film, but there is a crack.
C: The cured film has cracks, and there are also cracked parts.

<Pencil hardness>
About the cured film B produced on the acrylic resin board, pencil hardness was measured by the method (hand-drawing method) equivalent to JISK5600-5-4: 1999.

<Adhesion>
About the cured film B produced on each resin board, the presence or absence of peeling of a crosscut coating film was observed about 100 squares by the method equivalent to JISK5600-5-6, and the following reference | standard evaluated.
A: 99 or more crosscut coating films remain.
B: 81 to 98 sheets of crosscut coating film remained.
C: 50-80 sheets of cross-cut coating film remained.
D: The crosscut coating film remains 50 sheets or less.

<Flexibility>
The cured film C was wound around a rod of each diameter, and the presence or absence of cracks in the cured film was observed and evaluated according to the following criteria.
A: The cured film does not break even when wound around a rod having a diameter of 2 mm.
B: Although not cracked at φ4 mm, the cured film was cracked when wound around a φ2 mm rod.
C: Although not cracked at φ6 mm, the cured film was cracked when wound around a φ4 mm rod.
D: The cured film was cracked when wound around a rod having a diameter of 6 mm.

  Moreover, the raw material used by the Example and the comparative example is shown below.

(1) Polycarbonate diol (PCD1) Polycarbonate diol using isosorbide and 1,6-hexanediol as raw material diol (number average molecular weight: 880, OH number: 127)
In a 1 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, 1,6-hexanediol: 218.5 g, isosorbide: 264.4 g, diphenyl carbonate: 620.0 g, magnesium acetate tetrahydrate Product: 4.7 mg was put and nitrogen gas was replaced. The temperature was raised to an internal temperature of 160 ° C., and the contents were dissolved by heating and reacted for 1 hour. Thereafter, the reaction was performed while distilling off and removing phenol and unreacted diol while reducing the pressure to 0.27 kPa over 2 hours. Next, nitrogen gas bubbling was performed at 160 ° C. and 0.27 kPa for 1.5 hours to distill off phenol and unreacted diol. Further, while maintaining the pressure at 110 ° C. and 0.27 kPa, nitrogen gas was bubbled for 4 hours to remove phenol. The yield of the obtained polycarbonate diol product was 520.5 g.

  The hydroxyl value of the polycarbonate diol contained in the polycarbonate diol product is 127, the number average molecular weight (Mn) obtained from this hydroxyl value is 880, and the ratio (A) / (B) (isosorbide / 1,6-hexanediol) Is 49/51, terminal (A) / (B) ratio (terminal isosorbide / 1,6-hexanediol ratio) is 60/40, and terminal (A) ratio (I) calculated in (I) above. Was 1.22.

  The property of the obtained polycarbonate diol product was a transparent solid at room temperature. Further, the content of isosorbide as a raw material diol was 2.0% by mass, the phenol content was 0.06% by mass, and a polymer having a phenoxide terminal or a polymer containing an ether bond other than the isosorbide skeleton was not detected. Moreover, the residual diphenyl carbonate was below the limit of quantification (0.01% by mass or less). Furthermore, the average number of hydroxyl groups per molecule was 2.0.

(PCD2) Polycarbonate diol using isosorbide and 1,6-hexanediol as raw material diol (number average molecular weight: 900, OH value: 125)
In a 5 L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator, 1,6-hexanediol: 202.4 g, isosorbide: 750.9 g, diphenyl carbonate: 1046.8 g, magnesium acetate tetrahydrate Aqueous solution: 8.7 mL (concentration: 8.4 g / L, magnesium acetate tetrahydrate: 73 mg) was added, and the nitrogen gas was replaced. First, the internal temperature was raised to 130 ° C., and the contents were dissolved by heating. When the temperature was raised and dissolved, the pressure was lowered to 5.33 kPa over 5 minutes, and the reaction was carried out while distilling off phenol at 130 ° C. and 5.33 kPa for 240 minutes. Then, after reducing the pressure to 0.40 kPa over 120 minutes, the reaction was carried out while distilling off and removing phenol and unreacted diol while raising the temperature to 160 ° C. over 80 minutes. Finally, phenol and unreacted diol were distilled off at 160 ° C. and 0.40 kPa for 40 minutes to remove them. The yield of the obtained polycarbonate diol product was 989.2 g. Further, the obtained polycarbonate diol product was subjected to thin film distillation (temperature: 180 to 200 ° C., pressure: 0.027 kPa) at a flow rate of 20 g / min.

  The hydroxyl value of polycarbonate diol contained in the polycarbonate diol product after this thin-film distillation is 125, the number average molecular weight (Mn) obtained from this hydroxyl value is 900, and the ratio (A) / (B) (isosorbide / 1,6 -Hexanediol) is 76/24, the terminal (A) / (B) ratio (terminal isosorbide / 1,6-hexanediol ratio) is 91/9, and the terminal (A) calculated in (I) above. The rate (I) was 1.20.

  The property of the polycarbonate diol product after thin film distillation was a light yellow solid at room temperature. In addition, the content of isosorbide as a raw material diol was 2.5% by mass, and a phenol content, a polymer having a phenoxide terminal, and a polymer containing an ether bond other than the isosorbide skeleton were not detected. Moreover, the residual diphenyl carbonate was below the limit of quantification (0.01% by mass or less). Furthermore, the average number of hydroxyl groups per molecule was 2.0.

(PCD3) Polycarbonate diol using isosorbide and 1,6-hexanediol as raw material diol (number average molecular weight: 2100, OH value: 53.5)
In a 1 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, 1,6-hexanediol: 293.9 g, isosorbide: 121.2 g, diphenyl carbonate: 658.2 g, magnesium acetate tetrahydrate Product: 4.3 mg was charged and replaced with nitrogen gas. 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 performed while distilling off and removing phenol and unreacted diol while reducing the pressure to 0.27 kPa over 2 hours. Next, nitrogen gas bubbling was performed at 180 ° C. and 2.7 kPa for 15 minutes, and the reaction was conducted while distilling off and removing phenol and unreacted diol. After adding 400 g of o-dichlorobenzene, the reaction was continued for 5 hours at 130 ° C. while maintaining the pressure at 0.27 kPa, and then bubbled with nitrogen gas for 13 hours while maintaining the pressure at 2.7 kPa. A reaction for increasing the degree of polymerization of the diol was conducted. The yield of the obtained polycarbonate diol product was 454.2 g.

  The hydroxyl value of the polycarbonate diol contained in this polycarbonate diol product is 53.5, the number average molecular weight (Mn) obtained from this hydroxyl value is 2,100, the molecular weight distribution (Mw / Mn) is 1.96, (A ) / (B) ratio (isosorbide / 1,6-hexanediol) is 24/76, terminal (A) / (B) ratio (terminal isosorbide / 1,6-hexanediol ratio) is 62/38, The terminal (A) ratio (I) calculated in (I) was 2.58.

  The property of the obtained polycarbonate diol product was a viscous liquid at room temperature, and fluidity was observed. The viscosity (50 ° C.) was 24 Pa · s. Further, the content of isosorbide as a raw material diol was 0.5% by mass, and a polymer having a phenoxide terminal, a polymer containing an ether bond other than an isosorbide skeleton, phenol and o-dichlorobenzene were not detected. The residual diphenyl carbonate was below the limit of quantification (0.01% by mass or less). Furthermore, the average number of hydroxyl groups per molecule was 2.0.

(PCD4) Polycarbonate polyol using 3-methyl-1,5-pentanediol and 1,6-hexanediol as raw material diol in 9/1 (molar ratio) (number average molecular weight: 976, average hydroxyl value: 115 mgKOH / g , Trade name Kuraray polyol C-1090, manufactured by Kuraray Co., Ltd.)
(PCD5) Polycarbonate polyol (number average molecular weight: 920, average hydroxyl value: 125 mgKOH / g, alicyclic) using 1,4-cyclohexanedimethanol and 1,6-hexanediol as raw material polyols in 3/1 (molar ratio) Ratio of formula structure: 43% by mass, trade name: UM-CARB90 (3/1), manufactured by Ube Industries, Ltd.)
(PCD6) Polycarbonate polyol using 1,4-cyclohexanedimethanol as a raw material diol (number average molecular weight: 1002, average hydroxyl value: 112 mg KOH / g, trade name: ETENACOL UC-100, manufactured by Ube Industries).

(2) Polyether polyol (P1) 2-Butyl-2-ethyl-1,3-propanediol (Molecular weight: 160, trade name: BEPD, manufactured by PERSTORP)
(3) Organic polyisocyanate (IS1) Isophorone diisocyanate (molecular weight: 222, trade name: VESTANAT IPDI, manufactured by Degussa)
(IS2) 4,4′-dicyclohexylmethane diisocyanate (molecular weight: 262, trade name: Desmodur W, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
(IS3) Hexamethylene diisocyanate (molecular weight: 168, trade name: HDI, manufactured by Nippon Polyurethane Industry Co., Ltd.)
(IS4) 4,4′-diphenylmethane diisocyanate (Molecular weight: 250, trade name: Polymeric MDI, Dow Chemical Company)
(IS5) 1,3-bis (isocyanatomethyl) cyclohexane (molecular weight: 194, manufactured by Tokyo Chemical Industry Co., Ltd.)
(4) Hydroxyalkyl (meth) acrylate (HA1) 2-hydroxyethyl acrylate (molecular weight: 116, trade name: 2-hydroxyethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.)
(HA2) 2-hydroxyethyl methacrylate (molecular weight: 130, trade name: 2-hydroxyethyl methacrylate, manufactured by Nippon Shokubai Co., Ltd.)
(HA3) pentaerythritol triacrylate (molecular weight 279, saponification value 602.7, trade name: NK ester A-TMM-3, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(5) Active energy ray reactive monomer (E1) Pentaerythritol triacrylate (trade name: NK ester A-TMM-3, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(E2) Trimethylolpropane triacrylate (trade name: TMPTA, manufactured by Daicel Ornics)
(E3) Isobonyl acrylate (trade name: IBXA, manufactured by Osaka Organic Chemical Co., Ltd.)
(E4) Dipentaerythritol hexaacrylate (trade name: DPHA, manufactured by Daicel Ornics).

Example 1
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, nitrogen / oxygen blowing tube, 56.6 g of polycarbonate diol (PCD1, number average molecular weight: 880, OH number: 127), isophorone diisocyanate (polyisocyanate) 28.5 g of IS1, number average molecular weight: 222), 23.6 g of methyl ethyl ketone, and 0.009 g of bismuth tris (2-ethylhexanoate) were added, and the polycarbonate diol was reacted at 80 to 90 ° C. The completion of the reaction was confirmed by measuring NCO%.

  After completion of the reaction, after cooling to 60 ° C., 0.096 g of hydroquinone monomethyl ether (trade name: hydroquinone monomethyl ether, manufactured by Nacalai Tesque) as a polymerization inhibitor, 0.05 g of bismuth tris (2-ethylhexanoate), hydroxy As alkyl (meth) acrylate, 14.9 g of 2-hydroxyethyl acrylate (HA1, number average molecular weight: 116) is dropped, and the hydroxyalkyl (meth) acrylate is reacted at 80 to 90 ° C. to produce polycarbonate diol, polyisocyanate and hydroxy. A polyurethane (meth) acrylate oligomer having a ratio (molar ratio) to the alkyl (meth) acrylate of 1: 2: 2 was obtained. The completion of the reaction was confirmed by measuring NCO%. Table 1 shows the number average molecular weight of the obtained polyurethane (meth) acrylate oligomer and the molecular weight between calculated network crosslinking points.

  It is effective to blend the obtained polyurethane (meth) acrylate oligomer with pentaerythritol triacrylate (E1) as an active energy ray reactive monomer, Irgacure 184 (manufactured by BASF Japan) as a photopolymerization initiator, and ethyl acetate. An active energy ray-curable polymer composition in which the component amount (component amount other than the catalyst and the solvent) was adjusted to 40% was obtained. The ratio (mass ratio) between the polyurethane (meth) acrylate oligomer and the active energy ray-reactive monomer was 45/55. The photopolymerization initiator was blended so as to be 2 parts by mass relative to 100 parts by mass of the active ingredient.

Next, the active energy ray-curable polymer composition obtained above was poured into a polypropylene film box so that the cured film thickness was 400 μm, and dried using a hot air dryer at 60 ° C. for 120 minutes. . Thereafter, ultraviolet irradiation device (EYE GRANDAGE ECS-301, Eye Graphics Co., light source: metal halide) used, irradiation with 500 mJ / cm ^2, to prepare a cured film A.

Moreover, the active energy ray-curable polymer composition obtained above was applied to various resin plates shown in Table 1 so that the cured film thickness was 20 μm. Drying was performed at 60 ° C. for 10 minutes using a hot air dryer. Thereafter, ultraviolet irradiation device (EYE GRANDAGE ECS-301, Eye Graphics Co., light source: metal halide) used, irradiation with 500 mJ / cm ^2, to produce a cured film B.

Furthermore, the active energy ray-curable polymer composition obtained above was applied to a polyester film so that the cured film thickness was 20 μm. Drying was performed at 60 ° C. for 10 minutes using a hot air dryer. Thereafter, ultraviolet irradiation device (EYE GRANDAGE ECS-301, Eye Graphics Co., light source: metal halide) used, irradiation with 500 mJ / cm ^2, to produce a cured film C.

  As a result of measuring the tensile elongation at break, tensile strength at break, tensile elastic modulus and film formability of the obtained cured film A, pencil hardness (only cured film produced on an acrylic resin plate), adhesion Table 1 shows the results of measuring the flexibility and the results of measuring the flexibility of the cured film C.

(Examples 2 to 20)
In each example, polyurethane (meth) was obtained in the same manner as in Example 1 except that the polycarbonate diol, polyisocyanate, hydroxyalkyl (meth) acrylate, and active energy ray reactive monomer were changed to the compositions shown in Tables 1 to 4. An acrylate oligomer was obtained. Tables 1 to 4 show the number average molecular weight and molecular weight between calculated network cross-linking points of the obtained polyurethane (meth) acrylate oligomer. Next, the active energy was adjusted to 40% of the active ingredient amount (component amount other than the catalyst and the solvent) in the same manner as in Example 1 except that the polyurethane (meth) acrylate oligomer obtained in each Example was used. A linear curable polymer composition was obtained. Next, cured films A to C were produced in the same manner as in Example 1 using the active energy ray-curable polymer composition obtained in each Example. The cured film A obtained in each example was measured for tensile elongation at break, tensile strength at break, tensile elastic modulus and film formability. As a result, the cured film B obtained in each example was measured for pencil hardness (acrylic resin). Tables 1 to 4 show the results of measuring the flexibility of only the cured film produced on the plate), the results of measuring the adhesion, and the cured films C obtained in the examples.

(Comparative Example 1)
The polyurethane (meth) acrylate oligomer obtained in the same manner as in Example 1 was blended with Irgacure 184 (manufactured by BASF Japan) as a photopolymerization initiator and ethyl acetate, and the amount of active ingredients (components other than catalyst and solvent) An active energy ray-curable polymer composition having an amount adjusted to 40% was obtained. The photopolymerization initiator was blended so as to be 2 parts by mass with respect to 100 parts by mass of the active ingredient. Next, cured films A to C were produced in the same manner as in Example 1 using the obtained active energy ray-curable polymer composition. As a result of measuring the tensile elongation at break, tensile strength at break, tensile elastic modulus and film formability of the obtained cured film A, pencil hardness (only cured film produced on an acrylic resin plate), adhesion Table 5 shows the results of measuring the flexibility and the results of measuring the flexibility of the cured film C.

(Comparative Examples 2 to 5)
In each comparative example, the polyurethane (meth) acrylate type was the same as in Example 1 except that the polycarbonate diol, polyisocyanate, hydroxyalkyl (meth) acrylate, and active energy ray reactive monomer were changed to the compositions shown in Table 5. An oligomer was obtained. Table 5 shows the number average molecular weight and molecular weight between calculated network crosslinking points of the obtained polyurethane (meth) acrylate oligomer. Next, the active energy was adjusted to 40% of the active ingredient amount (component amount other than the catalyst and the solvent) in the same manner as in Example 1, except that the polyurethane (meth) acrylate oligomer obtained in each comparative example was used. A linear curable polymer composition was obtained. Next, cured films A to C were produced in the same manner as in Example 1 using the active energy ray-curable polymer composition obtained in each Comparative Example. The cured film A obtained in each comparative example was measured for tensile elongation at break, tensile breaking strength, tensile elastic modulus, and film formability. As a result, the cured film B obtained in each comparative example was measured for pencil hardness (acrylic resin). Table 5 shows the results of measuring the flexibility of the cured film C produced only on the plate), the results of measuring the adhesion, and the cured films C obtained in the respective comparative examples.

(Comparative Example 6)
Similar to Example 1 except that polyether polyol (P1, number average molecular weight: 160) was used instead of polycarbonate diol (PCD1), and polyisocyanate and hydroxyalkyl (meth) acrylate were changed to the compositions shown in Table 6. Thus, a polyurethane (meth) acrylate oligomer was obtained. Table 6 shows the number average molecular weight and molecular weight between calculated network crosslinking points of the obtained polyurethane (meth) acrylate oligomer. Next, an active energy ray-curable polymer composition in which the amount of active ingredients (components other than the catalyst and the solvent) was adjusted to 40% in the same manner as in Comparative Example 1 except that this polyurethane (meth) acrylate oligomer was used. I got a thing. Next, cured films A to C were produced in the same manner as in Example 1 using the obtained active energy ray-curable polymer composition. As a result of measuring the tensile elongation at break, tensile strength at break, tensile elastic modulus and film formability of the obtained cured film A, pencil hardness (only cured film produced on an acrylic resin plate), adhesion Table 6 shows the results of measuring the flexibility and the results of measuring the flexibility of the cured film C.

(Comparative Example 7)
Similar to Example 1 except that polyether polyol (P1, number average molecular weight: 160) was used instead of polycarbonate diol (PCD1), and polyisocyanate and hydroxyalkyl (meth) acrylate were changed to the compositions shown in Table 6. Thus, a polyurethane (meth) acrylate oligomer was obtained. Table 6 shows the number average molecular weight and molecular weight between calculated network crosslinking points of the obtained polyurethane (meth) acrylate oligomer. Next, an active energy ray-curable polymer composition in which the amount of active ingredients (components other than the catalyst and the solvent) was adjusted to 40% in the same manner as in Example 1 except that this polyurethane (meth) acrylate oligomer was used. I got a thing. Next, cured films A to C were produced in the same manner as in Example 1 using the obtained active energy ray-curable polymer composition. As a result of measuring the tensile elongation at break, tensile strength at break, tensile elastic modulus and film formability of the obtained cured film A, pencil hardness (only cured film produced on an acrylic resin plate), adhesion Table 6 shows the results of measuring the flexibility and the results of measuring the flexibility of the cured film C.

(Comparative Example 8)
Except that polycarbonate diol (PCD6, number average molecular weight: 1002) was used instead of polycarbonate diol (PCD1), and polyisocyanate and hydroxyalkyl (meth) acrylate were changed to the compositions shown in Table 6, the same procedure as in Example 1 was performed. Thus, a polyurethane (meth) acrylate oligomer was obtained. Table 6 shows the number average molecular weight and molecular weight between calculated network crosslinking points of the obtained polyurethane (meth) acrylate oligomer. Next, an active energy ray-curable polymer composition in which the amount of active ingredients (components other than the catalyst and the solvent) was adjusted to 40% in the same manner as in Comparative Example 1 except that this polyurethane (meth) acrylate oligomer was used. I got a thing. Next, cured films A to C were produced in the same manner as in Example 1 using the obtained active energy ray-curable polymer composition. As a result of measuring the tensile elongation at break, tensile strength at break, tensile elastic modulus and film formability of the obtained cured film A, pencil hardness (only cured film produced on an acrylic resin plate), adhesion Table 6 shows the results of measuring the flexibility and the results of measuring the flexibility of the cured film C.

(Comparative Example 9)
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen / oxygen blowing tube, pentaerythritol triacrylate (E1) as an active energy ray reactive monomer and Irgacure 184 (BASF Japan) as a photopolymerization initiator Product) and ethyl acetate were added to obtain an active energy ray-curable polymer composition in which the effective component amount (component amount other than the catalyst and the solvent) was adjusted to 40%. The photopolymerization initiator was blended so as to be 2 parts by mass with respect to 100 parts by mass of the active ingredient. Next, cured films A to C were produced in the same manner as in Example 1 using the obtained active energy ray-curable polymer composition. As a result of measuring the tensile elongation at break, tensile strength at break, tensile elastic modulus and film formability of the obtained cured film A, pencil hardness (only cured film produced on an acrylic resin plate), adhesion Table 6 shows the results of measuring the flexibility and the results of measuring the flexibility of the cured film C.

  As is clear from the results shown in Tables 1 to 4, the polyurethane (meth) acrylate oligomer according to the present invention is 1% by mass to 45% by mass and the active energy ray reactive monomer is 55% by mass to 99% by mass. The cured films (Examples 1 to 20) of the present invention produced using the active energy ray-curable polymer composition of the present invention contained in the above are excellent in flexibility while being high in hardness, and further, the substrate Have good adhesion.

  On the other hand, as is clear from the results shown in Tables 5 to 6, a cured film prepared using an active energy ray-curable polymer composition having a content of the active energy ray-reactive monomer of 50% by mass or less (comparison) Examples 1-3) were inferior in hardness. Moreover, when polycarbonate diol other than the polycarbonate diol concerning this invention is used (Comparative Examples 4-5, 8), the cured film obtained is inferior in hardness, and 3-methyl-1,5 as raw material diol. A cured film obtained when pentanediol and 1,6-hexanediol are used (Comparative Example 4) and when 1,4-cyclohexanedimethanol and 1,6-hexanediol are used (Comparative Example 5) Is inferior in adhesion to polyester, and when 1,4-cyclohexanedimethanol is used as a raw material diol (Comparative Example 8), the resulting cured film is inferior in flexibility. Moreover, when a polyether polyol is used instead of the polycarbonate diol according to the present invention (Comparative Examples 6 to 7), the resulting cured films are inferior in flexibility, and further, the active energy ray reactive monomer When not containing (Comparative Example 6), the obtained cured film was inferior in adhesion to polyester. Further, when the polyurethane (meth) acrylate oligomer according to the present invention was not contained (Comparative Example 9), the obtained cured film was inferior in film formability and flexibility.

  As described above, according to the present invention, it is possible to obtain a cured film that is excellent in flexibility while being high in hardness and having good adhesion to a substrate by irradiation with active energy rays. .

  Therefore, the active energy ray-curable polymer composition of the present invention is useful as a coating agent for flexible materials used in electronic devices and optical devices.

Claims (7)

The following general formula (A):
And the following general formula (B):
(In formula (B), X represents a C1-C15 divalent organic group which may contain a hetero atom.)
Activity containing a polyurethane (meth) acrylate oligomer which is a reaction product of a raw material containing polycarbonate diol, polyisocyanate, and hydroxyalkyl (meth) acrylate containing a repeating unit represented by An energy ray curable polymer composition comprising:
The polyurethane (meth) acrylate oligomer is contained at 1% by mass to 45% by mass with respect to 100% by mass of the active energy ray-curable polymer composition, and the active energy ray-reactive monomer is 55% by mass or more. An active energy ray-curable polymer composition comprising 99% by mass or less.   The polyurethane (meth) acrylate oligomer is contained in an amount of 5% by mass to 45% by mass with respect to 100% by mass of the active energy ray-curable polymer composition, and the active energy ray reactive monomer is 55% by mass or more. The active energy ray-curable polymer composition according to claim 1, which is contained in an amount of 95% by mass or less.   The active energy ray reactive monomer is at least one selected from the group consisting of aromatic vinyl monomers, vinyl ester monomers, vinyl ethers, allyl compounds, (meth) acrylamides, and (meth) acrylates. The active energy ray-curable polymer composition according to claim 1 or 2, wherein:   The polycarbonate diol contains 10% by mass or more of the repeating unit represented by the formula (A), the number average molecular weight of the polycarbonate diol is 500 or more and 5,000 or less, and the average number of hydroxyl groups per molecule is 2. The active energy ray-curable polymer composition according to any one of claims 1 to 3, wherein the active energy ray-curable polymer composition is .2 or less.   The active energy ray curable polymer composition according to any one of claims 1 to 4, further comprising an active energy ray polymerization initiator.   A cured film obtained by irradiating the active energy ray-curable polymer composition according to any one of claims 1 to 5 with an active energy ray.   A laminate comprising the layer made of the cured film according to claim 6.