JP2012122011A - Thiol compound, production method therefor and polymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerization initiator composition having high sensitivity, free from oxygen inhibition and excellent in water-resistance, alkali-resistance and heat-resistance, and to provide a new thiol compound containing the photopolymerization initiator composition and suitable for a photosensitive composition.SOLUTION: There are provided a polymerizable composition comprising a new aromatic ether-based polyfunctional primary thiol compound represented by general formula (1), a polymerizable composition comprising the aromatic ether-based polyfunctional primary thiol compound and a compound having an ethylenic unsaturated double bond, and cured products obtained by the photopolymerization of the composition. (In the formula, Rrepresents a single bond or a 1C-10C linear or branched alkylene; Rrepresents H or 1C-3C alkyl; Rrepresents H or 1C-3C alkyl; Rrepresents 1C-4C alkyl or alkoxy; (a) is 0 or 1; b is 3 or 4; c is an integer of 0-4; and a+b is 4).

Description

  The present invention relates to a novel thiol compound, a method for producing the thiol compound, and a polysynthetic composition containing the thiol compound. More specifically, a novel aromatic ether-based polyfunctional primary thiol compound used for a resin composition excellent in water resistance, alkali resistance and heat resistance, a method for producing the thiol compound, and a polysynthetic composition containing the thiol compound Related to things.

  Conventionally, polyfunctional thiol compounds have been widely used in various industrial fields such as halogen-based resin stabilizers, photosensitive compositions, and epoxy resin curing agents. Such polyfunctional thiol compounds can be classified into aliphatic ether type, aliphatic ester type and the like based on their chemical structures.

  Known aliphatic ethers include Toyo Co., Ltd. Thiocol LP (registered trademark), QE-340M, ADEKA Co., Ltd. EH-310, Cognis Co., Ltd. Capcure (registered trademark) 3-800, and the like. ing. Moreover, as an aliphatic ester type | system | group, Sakai Chemical Co., Ltd. TMMP, ADEKA Co., Ltd. EH-317, Japan Epoxy Resin Co., Ltd. QX-40, Showa Denko Co., Ltd. Karenz MT (trademark) PE1 Karenz MT (registered trademark) BD1, Karenz MT (registered trademark) NR1, and the like are known.

  Among the uses of polyfunctional thiols, photosensitive compositions are used in various fields such as coatings, adhesives, printing plates, color proofs, color filters, solder resists, and photocurable inks. In recent years, in particular, from the viewpoints of environmental problems including these applications, energy saving, work safety, production cost, etc., the characteristics of photocuring such as curing at room temperature in a short time and no need for solvents have been attracting attention. Many researches and developments have been made on sexual compositions.

  Furthermore, in the coating field, there is an increasing demand for resin compositions that are easy to mold, have high impact resistance, and are excellent in water resistance.

  When used in a thiol / ene curable resin composition, the polyfunctional thiol compound has features such as no oxygen inhibition, a small amount of initiator used, low curing shrinkage, and high sensitivity. Therefore, various uses have been developed. However, the conventional aliphatic ester-based polyfunctional thiol has an ester structure and thus has a drawback of poor water resistance. Moreover, since the conventional aliphatic ether thiol disclosed in JP-A-9-043907 (Patent Document 1) has a flexible structure, it has a drawback of low glass transition temperature.

  Studies are being conducted to eliminate these drawbacks. Japanese Patent Application Laid-Open No. 2007-70417 (Patent Document 2) discloses a photocuring monomer comprising a polymercaptocarboxylic acid amide. In order to improve the water resistance of a conventional ester-based polyfunctional thiol compound, an amide-based monomer is disclosed. The polyfunctional thiol is used to eliminate the drawbacks.

Japanese Patent Laid-Open No. 9-043907 JP 2007-70417 A

  The present invention relates to a photopolymerization initiator composition which is highly sensitive and free from oxygen inhibition and excellent in water resistance, alkali resistance and heat resistance, and a novel thiol compound suitable for a photosensitive composition containing the photopolymerization initiator composition It is an issue to provide.

  The present inventors have found that the above problems can be solved by using a novel polyfunctional thiol compound of an aromatic ether type having a primary mercapto group as a component of a photopolymerization initiator composition. The present invention has been completed.

（式中、Ｒ¹は単結合または炭素数１〜１０の直鎖状または分岐状のアルキレン基を表し、Ｒ²は水素原子または炭素数１〜３のアルキル基を表し、Ｒ³は水素原子または炭素数１〜３のアルキル基を表し、Ｒ⁴は炭素数１〜４のアルキル基またはアルコキシ基を表し、ａは０または１であり、ｂは３または４であり、ｃは０〜４の整数であり、ａ＋ｂは４である。）
で示される芳香族エーテル系多官能一級チオール化合物。
［２］前記一般式（１）において、ａ＝１、ｂ＝３である前記［１］に記載の芳香族エーテル系多官能一級チオール化合物。
［３］前記一般式（１）において、Ｒ¹が主鎖の炭素数が１または２の、直鎖状または分岐状のアルキレン基である前記［１］に記載の芳香族エーテル系多官能一級チオール化合物。
［４］前記一般式（１）において、Ｒ¹がメチレン基、Ｒ³が水素原子またはメチル基、ｃ＝０である前記［１］に記載の芳香族エーテル系多官能一級チオール化合物。
［５］前記一般式（１）で示される化合物が、トリス（４−（３−メルカプトプロポキシ）フェニル）メタン、１，１，１−トリス（４−（３−メルカプトプロポキシ）フェニル）エタン、またはテトラキス（４−（３−メルカプトプロポキシ）フェニル）メタンである前記［１］に記載の芳香族エーテル系多官能一級チオール化合物。
［６］一般式（１）

（式中、Ｒ¹は単結合または炭素数１〜１０の直鎖状または分岐状のアルキレン基を表し、Ｒ²は水素原子または炭素数１〜３のアルキル基を表し、Ｒ³は水素原子または炭素数１〜３のアルキル基を表し、Ｒ⁴は炭素数１〜４のアルキル基またはアルコキシ基を表し、ａは０または１であり、ｂは３または４であり、ｃは０〜４の整数であり、ａ＋ｂは４である。）
で示される芳香族エーテル系多官能一級チオール化合物と、エチレン性不飽和二重結合を有する化合物とを含むことを特徴とする重合性組成物。
［７］エチレン性不飽和二重結合を有する官能基が、アクリロイルオキシ基、メタアクリロイルオキシ基、アリル基、ビニルオキシ基、スチリル基からなる群から選ばれる少なくとも１種であり、エチレン性不飽和二重結合を有する化合物がこれらの官能基を少なくとも２個有する化合物である前記［６］に記載の重合性組成物。
［８］光重合開始剤を含む前記［６］または［７］に記載の重合性組成物。
［９］重合禁止剤を含む前記［６］〜［８］のいずれかに記載の重合性組成物。
［１０］二級アミンまたは三級アミンを含む前記［６］〜［９］のいずれかに記載の重合性組成物。
［１１］前記［６］〜［１０］のいずれかに記載の重合性組成物を重合して得られる硬化物。
［１２］一般式（２）

（式中、Ｒ³は水素原子または炭素数１〜３のアルキル基を表し、Ｒ⁴は炭素数１〜４のアルキル基またはアルコキシ基を表し、ａは０または１であり、ｂは３または４であり、ｃは０〜４の整数であり、ａ＋ｂは４である。）
で示される多価フェノール化合物と、一般式（３）

（式中、Ｒ¹は単結合または炭素数１〜１０の直鎖状または分岐状のアルキレン基を表し、Ｒ²は水素原子または炭素数１〜３のアルキル基を表し、Ｘは脱離基を表す。）
で示される化合物を反応させて一般式（４）

（式中の記号は、前記式（２）および式（３）の定義と同じ意味を表す。）
で示される末端二重結合含有化合物を得る工程１、
前記末端二重結合含有化合物の二重結合部位にメルカプト基を付加する工程２
を含むことを特徴とする、一般式（１）

（式中の記号は前記と同じ意味を表す。）
で示される芳香族エーテル系多官能一級チオール化合物の製造方法。
［１３］前記一般式（３）において、Ｘがハロゲン、またはスルホネート基である前記［１２］に記載の芳香族エーテル系多官能一級チオール化合物の製造方法。 The present invention relates to the following novel polyfunctional primary thiol compound, a production method thereof, a polymerizable composition, and a cured product obtained by polymerizing the composition.
[1] General formula (1)

(In the formula, R ¹ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³ represents a hydrogen atom. Or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group or alkoxy group having 1 to ⁴ carbon atoms, a is 0 or 1, b is 3 or 4, and c is 0 to 4 And a + b is 4.)
An aromatic ether-based polyfunctional primary thiol compound represented by
[2] The aromatic ether-based polyfunctional primary thiol compound according to [1], wherein a = 1 and b = 3 in the general formula (1).
[3] The aromatic ether polyfunctional primary according to the above [1], wherein in the general formula (1), R ¹ is a linear or branched alkylene group having 1 or 2 carbon atoms in the main chain. Thiol compound.
[4] The aromatic ether polyfunctional primary thiol compound according to [1], wherein in general formula (1), R ¹ is a methylene group, R ³ is a hydrogen atom or a methyl group, and c = 0.
[5] The compound represented by the general formula (1) is tris (4- (3-mercaptopropoxy) phenyl) methane, 1,1,1-tris (4- (3-mercaptopropoxy) phenyl) ethane, or The aromatic ether polyfunctional primary thiol compound according to the above [1], which is tetrakis (4- (3-mercaptopropoxy) phenyl) methane.
[6] General formula (1)

(In the formula, R ¹ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³ represents a hydrogen atom. Or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group or alkoxy group having 1 to ⁴ carbon atoms, a is 0 or 1, b is 3 or 4, and c is 0 to 4 And a + b is 4.)
A polymerizable composition comprising an aromatic ether-based polyfunctional primary thiol compound represented by formula (II) and a compound having an ethylenically unsaturated double bond.
[7] The functional group having an ethylenically unsaturated double bond is at least one selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an allyl group, a vinyloxy group, and a styryl group. The polymerizable composition according to [6], wherein the compound having a heavy bond is a compound having at least two of these functional groups.
[8] The polymerizable composition as described in [6] or [7], including a photopolymerization initiator.
[9] The polymerizable composition according to any one of [6] to [8], including a polymerization inhibitor.
[10] The polymerizable composition as described in any one of [6] to [9], including a secondary amine or a tertiary amine.
[11] A cured product obtained by polymerizing the polymerizable composition according to any one of [6] to [10].
[12] General formula (2)

(Wherein R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group or alkoxy group having 1 to ⁴ carbon atoms, a is 0 or 1, and b is 3 or 4 and c is an integer from 0 to 4 and a + b is 4.)
A polyhydric phenol compound represented by the general formula (3)

(In the formula, R ¹ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents a leaving group. Represents.)
Is reacted with a compound of the general formula (4)

(The symbols in the formula have the same meaning as defined in the formulas (2) and (3).)
Step 1 for obtaining a compound containing a terminal double bond represented by:
Step 2 of adding a mercapto group to the double bond site of the compound containing a terminal double bond
General formula (1), characterized in that

(The symbols in the formula have the same meaning as described above.)
The manufacturing method of the aromatic ether type polyfunctional primary thiol compound shown by these.
[13] The method for producing an aromatic ether polyfunctional primary thiol compound according to the above [12], wherein, in the general formula (3), X is a halogen or a sulfonate group.

  Since the polyfunctional primary thiol compound of the present invention has a specific aromatic ether type structure, when used as a curing agent for thiol / ene curing, the cured product has good water resistance and alkali resistance.

When the photopolymerization initiator composition containing the thiol compound of the present invention is used, a photosensitive composition having high sensitivity, no oxygen inhibition, and excellent water resistance, alkali resistance and heat resistance can be obtained.
The photosensitive composition using the thiol compound of the present invention is suitable for application fields such as coating compositions, adhesives, resists for photoengraving, solder resists, etching resists, color filter resists, holograms, stereolithography, and UV inks. Used.

¹ H-NMR spectrum of tris (4- (3-mercaptopropoxy) phenyl) methane (TP-T1) obtained in Example 1. ¹³ C-NMR spectrum of TP-T1 obtained in Example 1. FIG.

[I] Aromatic ether-based polyfunctional primary thiol compound The thiol compound of the present invention is a thiol compound having a specific mercapto group-containing group, and the mercapto group-containing group is a primary mercapto group represented by the following general formula (1 ) (Hereinafter sometimes abbreviated as “aromatic ether polyfunctional thiol compound (1)”).

In the general formula (1), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, and may have a substituent.

Examples of the linear or branched alkylene group having 1 to 10 carbon atoms represented by R ¹ include a methylene group, an ethylene group, an n-propylene group, an iso-propylene group, an n-butylene group, an iso-butylene group, Examples include t-butylene group, n-hexylene group, n-octylene group, n-decanylene group and the like.

As the linear or branched alkylene group having 1 to 10 carbon atoms represented by R ^1, from the viewpoint of being able to produce the thiol compound of the general formula (1) using a highly reactive raw material, 1-5 are preferable and, as for carbon number, 1-2 are more preferable. Specifically, a methylene group and an ethylene group are preferable.

In the general formula (1), R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may have a substituent.
Examples of the alkyl group having 1 to 3 carbon atoms represented by R ² include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group.
R ² is preferably a hydrogen atom, a methyl group or an ethyl group.

In the general formula (1), R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may have a substituent.
Examples of the alkyl group having 1 to 3 carbon atoms represented by R ³ include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group.
R ³ is preferably a hydrogen atom, a methyl group or an ethyl group.

In the general formula (1), R ⁴ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and may have a substituent.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a t-butyl group, preferably a methyl group, t-Butyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ⁴ include a methoxy group, an ethoxy group, an iso-propoxy group, a t-butoxy group, and the like, preferably a methoxy group and an ethoxy group.

Examples of the substituent which the alkyl group or alkoxy group represented by R ¹ , R ² , R ³ and R ⁴ may have include a methoxy group, an ethoxy group, a hydroxyl group and a dimethylamino group.

In the general formula (1), a is 0 or 1, b is 3 or 4, and a + b is 4. From the viewpoint of the structural stability of the thiol compound represented by the general formula (1), it is preferable that a = 1 and b = 3.
In the general formula (1), c is an integer of 0 to 4.

  The thiol compound of the present invention represented by the general formula (1) is derived from an aromatic compound (polyhydric phenol compound) having 3 to 4 phenolic hydroxyl groups, and the aromatic group is obtained by removing the hydrogen atom of the phenolic hydroxyl group. Has a skeleton.

  As an aromatic compound (polyhydric phenol compound) having 3 to 4 phenolic hydroxyl groups, for example, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, tetrakis (4 -Hydroxyphenyl) methane can be used, but is not limited thereto.

The thiol compound having the structure of the general formula (1) of the present invention is a thiol wherein R ¹ is a methylene group and R ² and R ⁴ are hydrogen atoms from the viewpoint that an easily available raw material can be used. More preferred are compounds.

  Specific examples of the thiol compound having the structure of the general formula (1) of the present invention include tris (4- (2-mercaptopropoxy) phenyl) methane, 1,1,1-tris (4- (2-mercaptopropoxy). ) Phenyl) ethane and tetrakis (4- (2-mercaptopropoxy) phenyl) methane.

（式中の記号は、一般式（１）の記号と同じ意味を表す。）
で示される多価フェノール化合物（以下、多価フェノール化合物（２）と略記することがある。）と、一般式（３）

（式中、Ｒ¹およびＲ²は一般式（１）の記号と同じ意味を表し、Ｘは脱離基を表す。）
で示される化合物を反応させる一般式（４）

（式中の記号は、一般式（１）の記号と同じ意味を表す。）
で示される末端二重結合を含有する化合物（以下、末端二重結合含有化合物（４）と略記することがある。）を得る工程１、および前記末端二重結合含有化合物の二重結合部位にメルカプト基を付加する工程２を含む方法が挙げられる。 [II] Method for Producing Thiol Compound The method for producing the thiol compound of the present invention is not particularly limited, but a method using a polyhydric phenol compound as a raw material is preferably used. As a method for producing the thiol compound of the present invention from a polyhydric phenol compound,
General formula (2)

(The symbols in the formula have the same meaning as the symbols in the general formula (1).)
A polyhydric phenol compound represented by formula (hereinafter sometimes abbreviated as polyhydric phenol compound (2)), and general formula (3).

(In the formula, R ¹ and R ² represent the same meaning as the symbol in general formula (1), and X represents a leaving group.)
A compound represented by the general formula (4)

(The symbols in the formula have the same meaning as the symbols in the general formula (1).)
Step 1 to obtain a compound containing a terminal double bond represented by (hereinafter sometimes abbreviated as a terminal double bond-containing compound (4)), and the double bond site of the terminal double bond-containing compound The method of including the process 2 of adding a mercapto group is mentioned.

In general formula (3), the leaving group represented by X refers to any group leaving from general formula (3), and —NR ⁵ ₂ (R ⁵ is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or Aryl group); sulfonates including alkyl sulfonates including methane sulfonate, etc., fluoroalkyl sulfonates including trifluoromethane sulfonate, etc., aryl sulfonates including tosylate, etc .; carbonates; halogens; carboxylates; phenolates; alkoxides; N-hydroxysuccinimides N-hydroxybenzotriazole and the like. Preferred examples of the leaving group include halogen and sulfonate. From the viewpoint of reactivity and availability of raw materials, bromine, chlorine and iodine are preferable as halogen, and trifluoromethanesulfonate and methanesulfonate are preferable as sulfonate. preferable.

  The reaction of the polyphenol compound (2) and the compound represented by the general formula (3) in Step 1 is preferably performed under basic conditions from the viewpoint of yield.

  Although the basic compound used in order to carry out on basic conditions is not specifically limited, An organic base and an inorganic base can be used. As the inorganic base, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate and the like can be used. Among them, sodium hydroxide is easy to adjust basic conditions and is more preferable in terms of reactivity. is there. As the organic base, tertiary amines such as triethylamine, pyridine and triethylenediamine can be preferably used.

  In step 1, the reaction molar ratio of the polyhydric phenol compound (2) and the compound represented by the general formula (3) is not particularly limited, but preferably the general formula (3) with respect to the hydroxyl group of the polyhydric phenol compound (2). ) Can be used in an amount of 0.9 to 2.0 equivalents, more preferably 1.0 to 1.2 equivalents. Moreover, the usage-amount of a basic compound can use 0.9-3.0 equivalent suitably with respect to the compound shown by General formula (3), More preferably, it is 1.0-1.2. Equivalent amounts can be used.

  In step 1, a solvent can be used to facilitate handling of the raw materials and products, and to facilitate contact between the raw materials and the basic compound. As the solvent, there can be used a raw material and a solvent which does not react with the product and has a boiling point capable of being distilled under normal conditions. Specifically, examples of the highly water-soluble solvent include dimethyl sulfoxide, acetone, tetrahydrofuran, tetrahydropyran and the like. Among them, dimethyl sulfoxide is preferable from the viewpoint of boiling point and raw material solubility.

  In step 1, the reaction temperature is not particularly limited, but is preferably performed at a temperature of 0 to 120 ° C. from the viewpoint of the solubility of the raw materials and the boiling point of the solvent. Furthermore, it is more preferable to carry out the reaction at a temperature in the vicinity of the boiling point of the solvent (boiling point minus 10 ° C. to boiling point) from the viewpoint of controlling the reaction temperature.

In Step 2, the step of adding a mercapto group to the terminal double bond site of the terminal double bond-containing compound (4) obtained in Step 1 includes the following two steps.
(1) Step 2-1, in which thioacetic acid is added to the terminal double bond site of the terminal double bond-containing compound (4) to form a thioacetate ester,
(2) Step 2-2 for hydrolyzing the thioacetate group to convert it to a mercapto group.

  The amount of thioacetic acid used in Step 2-1 for obtaining a thioacetic acid ester is preferably 1.0 to 3.0 mol with respect to 1 mol of the terminal double bond group in the terminal double bond-containing compound (4). 0 to 1.2 mol is more preferable.

  In step 2-1, a radical initiator may be used. Specific examples of the radical initiator include 2,2′-azobisisobutyronitrile, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (1-acetoxy-1-phenylethane), dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-amidinopropane) dihydrochloride, etc. Perazo initiators, benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethylhexanoate, hydroperoxide, di (2-ethylhexyl) peroxydicarbonate, etc. Examples thereof include, but are not limited to, oxides. From the viewpoint of reactivity, an azo initiator is preferable, and 2,2'-azobisisobutyronitrile is more preferable.

  In step 2-1, a solvent can be used to facilitate contact of the raw materials. As the solvent, there can be used a raw material and a solvent which does not react with the product and has a boiling point capable of being distilled under normal conditions. Specifically, from the viewpoint of solubility of raw materials, tetrahydrofuran, tetrahydropyran, toluene, xylene and the like are preferable, dehydrated tetrahydrofuran is more preferable, and dehydrated tetrahydrofuran not containing a stabilizer is more preferable.

  In step 2-1, the reaction temperature is not particularly limited, but it is preferably performed at 0 to 150 ° C. in order to control the reaction rate. Furthermore, from the point which suppresses a side reaction, 10-120 degreeC is more preferable, and it is most preferable to carry out at 50-100 degreeC.

  In Step 2-2, as a step of hydrolyzing the thioacetic acid ester to convert it into a mercapto group, a generally performed hydrolysis reaction can be used. Although the basic compound used in order to carry out on basic conditions is not specifically limited, An organic base and an inorganic base can be used. As the inorganic base, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate and the like can be used. Among them, sodium hydroxide is easy to adjust basic conditions and is more preferable in terms of reactivity. is there.

  In step 2-2, the amount of the basic compound used is not particularly limited, but it is preferably used in an equivalent amount or more, more preferably 1.0 to 1.5 equivalents, relative to the thioacetate group.

  In Step 2-2, a solvent can be used to facilitate handling of the raw material and the product and to facilitate contact between the raw material and the basic compound. As the solvent, a solvent that does not react with the raw materials and products and has a boiling point that can be distilled under normal conditions can be used. Specific examples include hydrophobic solvents such as tetrahydrofuran, tetrahydropyran, toluene, and xylene. Of these, tetrahydrofuran and tetrahydropyran are preferred from the viewpoint of boiling point and raw material solubility.

  In step 2-2, a hydrophilic solvent may be added for the purpose of promoting the reaction between the hydrophobic raw material and the basic compound. As the solvent, alcohol or acetone having high hydrophilicity is preferable, and ethanol is more preferable from the viewpoint of boiling point and solubility of raw materials.

  In step 2-2, the reaction temperature is not particularly limited, but it is preferably performed at 0 to 150 ° C. in order to control the reaction temperature. Furthermore, from the point which suppresses a side reaction, 10-120 degreeC is more preferable, and it is most preferable to carry out at 50-100 degreeC.

  As a method for isolating the product after step 2-2, a general isolation method such as distillation, recrystallization, organic solvent extraction, column chromatography, etc. can be used according to the substrate. Among these, it is preferable to use organic solvent extraction in order to separate from the inorganic salt by-produced in Step 2-1 and Step 2-2. The organic solvent used in the organic solvent extraction is not particularly limited as long as it is a solvent having low compatibility with water and can be distilled off under normal conditions. Specifically, toluene, chloroform, methylene chloride, ethyl acetate and the like can be used. Purification may be performed by column chromatography after extraction with an organic solvent.

[III] Compound having an ethylenically unsaturated double bond Although the compound having an ethylenically unsaturated double bond used in the polymerizable composition of the present invention is not particularly limited, the aromatic ether polyfunctional primary thiol compound (1 ), A compound having at least one functional group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an allyl group, a vinyloxy group, and a styryl group is preferable, and the curing rate is high. A compound having two or more functional groups in the molecule is preferred because of its high sensitivity.

  Specific examples of the compound having an ethylenically unsaturated double bond used in the present invention include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triallyl ether, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate. , Pentaerythritol tetraallyl ether, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2,2-bis (4- (2-acryloyloxyethyl) phenyl) propane, 2,2-bis (4- (2-methacryloyl) Oxyethyl) phenyl) propane, 2,2-bis (4-allyloxyphenyl) propane, divinylbenzene, diisopropenylbenzene and the like. The present invention is not limited. The amount of the compound having an ethylenically unsaturated double bond used in the present invention is generally 1 to 2 with respect to the thiol functional group of the aromatic ether polyfunctional primary thiol compound (1). It can be used 1000 times, preferably 1 to 100 times, more preferably 5 to 20 times. When it is more than 1000 times, the effect of adding the aromatic ether polyfunctional primary thiol compound (1) does not appear remarkably, and when it is less than 1 time, the unreacted aromatic ether polyfunctional primary thiol compound (1) is produced. Since it remains in the cured product, the mechanical properties of the cured product are poor.

[IV] Photopolymerization initiator The polymerizable composition of the present invention contains a photopolymerization initiator. The addition amount of the photopolymerization initiator is preferably 0.1 to 10% by mass and more preferably 1 to 5% by mass with respect to the entire composition. When a large amount of the photopolymerization initiator is used, the storage stability of the composition is lowered, and when the amount of the photopolymerization initiator is small, the curability is deteriorated. Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methylbenzoyl formate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylthiu Examples thereof include sulfur compounds such as mudisulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and the like. ) Can be suitably used. These photopolymerization initiators may be used alone or in combination of two or more.

[V] Other Additives A polymerization inhibitor may be added to the polymerizable composition of the present invention as necessary. The polymerization inhibitor has the effect of increasing the storage stability of the composition, but if too much is added, the curability deteriorates. As for the addition amount of a polymerization inhibitor, it is preferable to add 10-50000 mass ppm with respect to polymeric composition, and it is more preferable to add 100-5000 mass ppm. Specific examples of the polymerization inhibitor used in the present invention include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-t- Examples include but are not limited to butyl-p-methylphenol, chloranil, pyrogallol and the like.

  A secondary or tertiary amine may be added to the polymerizable composition of the present invention as necessary. These amines have an effect of increasing the reactivity between an aromatic ether-based polyfunctional primary thiol compound and a compound having an ethylenically unsaturated double bond. Moreover, there exists an effect as a chain transfer agent. The amount of secondary or tertiary amine added to the polymerizable composition of the present invention is not particularly limited, but is 0.1 to 5% by mass, preferably 1 to 5% by mass, based on the entire composition. Specific examples of the secondary or tertiary amine used in the present invention include, but are not limited to, diethylamine, triethylamine, diethanolamine, triethanolamine, N, N-dimethylbenzylamine, N, N-dimethylaniline and the like. Is not to be done.

  If necessary, the polymerizable composition of the present invention includes (a) a thermoplastic resin, (b) a deodorizing agent, (c) an adhesion improver such as a silane coupling agent and a titanium coupling agent, (d) Antioxidants such as hindered amines, hydroquinones, hindered phenols, (e) UV absorbers such as benzophenones, benzotriazoles, salicylic acid esters, metal complex salts, (f) metal soaps, heavy metals (eg zinc , Tin, lead, cadmium, etc.) inorganic and organic salts, stabilizers such as organic tin compounds, (g) phthalates, phosphates, fatty acids, epoxidized soybean oil, castor oil, liquid paraffin alkyl polycyclic aromatics Plasticizers such as hydrocarbons, (h) paraffin wax, microcrystalline wax, polymer wax, beeswax, whale wax low molecular weight polyolefin Waxes such as (i) non-reactive diluents such as benzyl alcohol, tar and pitumen, (j) calcium carbonate, kaolin, talc, mica, bentonite, clay, sericite, glass fiber, carbon fiber, aramid fiber, Filler such as nylon fiber, acrylic fiber, glass powder, glass balloon, shirasu balloon, coal powder, acrylic resin powder, phenol resin powder, metal powder, ceramic powder, zeolite, slate powder, (k) carbon black, titanium oxide, Pigments or dyes such as red iron oxide, para red, and bitumen, (l) solvents such as ethyl acetate, toluene, alcohols, ethers, ketones, (m) blowing agents, (n) silane coupling agents, monoisocyanate compounds , Dehydrating agents such as carbodiimide compounds, (o) antistatic agents, (p) antibacterial agents, (q Fungicide, (r) viscosity modifier, (s) fragrance, (t) a flame retardant, (u) a leveling agent, may be added (v) dispersing agent. These may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

  The method for curing the polymerizable composition of the present invention is not particularly limited, and a generally used method for curing the polymerizable composition can be used. As a curing method, when coating is performed, the polymerizable composition of the present invention is applied on a base film, and the coating is cured by applying ultraviolet irradiation to perform coating. When producing a film or sheet, the film or sheet can be produced by sandwiching the polymerizable composition of the present invention between a base film and a cover film and performing ultraviolet irradiation. A glass plate may be used instead of the base film or the cover film. In order to prevent oxygen inhibition during curing, curing can also be performed in an inert gas atmosphere.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example and a reference example, this invention is not restrict | limited at all by the following example. In the following examples, parts and% are based on mass.

Example 1: Synthesis of tris (4- (3-mercaptopropoxy) phenyl) methane (TP-T1)

Step 1: Synthesis of tris (4-allylphenyl) methane (TP-Allyl) 6L of tris (4-hydroxyphenyl) methane (Tokyo Kasei Co., Ltd. reagent), 200 ml of dimethyl sulfoxide and 1 L of eggplant The flask was charged and the contents were stirred at room temperature under a nitrogen atmosphere. While the raw material was dissolved, 27.1 g of a 50% by mass aqueous sodium hydroxide solution was added while cooling to 0 ° C., and 82.0 g (0.68 mol) of allyl bromide was added dropwise over 15 minutes, followed by returning to room temperature and stirring for 45 minutes. After confirming the disappearance of the raw materials by thin layer chromatography, 3 mL of concentrated hydrochloric acid was added to make the system acidic. The reaction solution was washed successively with water and saturated brine, and the organic layer was extracted and evaporated with ethyl acetate. It dried with the vacuum pump and obtained TP-Allyl. The obtained TP-Allyl was a yellow liquid, and the yield was 78.5 g and the yield was 93%. The composition formula of TP-Allyl is C28H28O3 and the molecular weight is 412.520.

Step 2-1: Synthesis of tris (4- (1- (acetylsulfanyl) propoxy) phenyl) methane (TP-SAc) TP-Allyl 10.0 g (24 mmol), dehydrated tetrahydrofuran 100 mL (without stabilizer) 4 The flask was charged into a 300 mL eggplant flask and equipped with a cooling tube, and then heated and stirred at 80 ° C. while carrying out nitrogen bubbling. Azobisisobutyronitrile (0.40 g, 2.4 mmol) was added in three portions within one and a half hours. Separately from the reaction system, 6.64 g (87.3 mmol) of thioacetic acid and 10 mL of dehydrated tetrahydrofuran (containing no stabilizer) were added to a two-necked 20 mL eggplant flask and subjected to nitrogen bubbling for 1 hour and a half to obtain a thioacetic acid / tetrahydrofuran solution. Was prepared. Two hours after the addition of azobisisobutyronitrile, the thioacetic acid / tetrahydrofuran solution mixed in a two-necked 20 mL eggplant flask was added dropwise in three portions within 1 hour. The mixture was stirred with heating for 50 hours and then at room temperature for 3 days, and disappearance of the raw materials and intermediates was confirmed by liquid chromatography. The reaction solution was neutralized with an aqueous sodium hydroxide solution, washed successively with an aqueous sodium hydroxide solution and saturated brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate, ethyl acetate was distilled off and dried with a vacuum pump to obtain TP-SAc. The obtained TP-SAc was a yellow liquid, and the yield was 8.5 g and the yield was 55%. The composition formula of TP-SAc is C34H40O6S3.

Step 2-2: Synthesis of tris (4- (3-mercaptopropoxy) phenyl) methane (TP-T1) 40.0 g of TP-Allyl 60.0 g (0.15 mol) and dehydrated tetrahydrofuran 300 mL (containing no stabilizer) The flask was charged into a 1 L eggplant flask, fitted with a cooling tube, and heated and stirred at 80 ° C. while performing nitrogen bubbling. Stirring was continued after adding 1.76 g (10.7 mmol) of azobisisobutyronitrile. Separately, 36.7 g (0.48 mmol) of thioacetic acid and dehydrated tetrahydrofuran (containing no stabilizer) were mixed in a 2-neck 200 mL eggplant flask and nitrogen bubbling was performed for 2 hours. Three and a half hours after addition of azobisisobutyronitrile, a thioacetic acid / dehydrated tetrahydrofuran solution was added dropwise over 30 minutes. After completion of the dropwise addition, 0.56 g (3.8 mmol) of azobisisobutyronitrile was added. While confirming the progress of the reaction by liquid chromatography, azobisisobutyronitrile 4 times (total 1.29 g) and thioacetic acid 1 time (3 mL) were added and reacted for a total of 60 hours for a total of 15 days.
After confirming disappearance of the raw materials and intermediates, the temperature was returned to room temperature, 20 mL of ethanol and 88.5 g of 20 mass% sodium hydroxide were added, and the mixture was heated and stirred at 80 ° C. After 2 hours, the mixture was neutralized with a saturated aqueous potassium hydrogen sulfate solution, and water was added to the precipitate formed at the bottom to dissolve it. The reaction solution was extracted with ethyl acetate and further washed with saturated brine. At this time, nitrogen was blown in to avoid contact with air as much as possible. Ethyl acetate was distilled off from the extracted organic layer and dried with a vacuum pump to obtain TP-T1.

１．３７ｐｐｍ：ｔｄ；３Ｈ；チオール基の水素原子、
２．０４ｐｐｍ：ｔｔ；６Ｈ；９、９'、９''の炭素につく水素原子、
２．７１ｐｐｍ：ｔ；６Ｈ；１０、１０'、１０''の炭素につく水素原子、
４．０３ｐｐｍ：ｔ；６Ｈ；８、８'、８''の炭素につく水素原子、
６．７９ｐｐｍ：ｄ；６Ｈ；芳香環につく水素原子、
６．９８ｐｐｍ：ｄ；６Ｈ；芳香環につく水素原子。
［¹³Ｃ−ＮＭＲ］
ＴＰ−Ｔ１の¹³Ｃ−ＮＭＲチャートを図２に示した。¹³Ｃ−ＮＭＲは、ＪＥＯＬ社製ＡＬ４００を使用し、重クロロホルム中にて測定を行った。
２１．０ｐｐｍ、３３．０ｐｐｍ：９、９'、９''、１０、１０'、１０''の炭素原子、
５４．０ｐｐｍ：１の炭素原子、
１１３．７ｐｐｍ、１２９．７ｐｐｍ、１３６．４ｐｐｍ：２、２'、２''、３，３'、３''、４，４'、４''、６，６'、６''、７，７'、７''の炭素原子、
１５６．６ｐｐｍ：５，５'、５''の炭素原子。 Structural analysis:
(1) TP-T1
[ ¹ H-NMR]
A ¹ H-NMR chart of TP-T1 is shown in FIG. ¹ H-NMR was measured in deuterated chloroform using AL400 manufactured by JEOL.

1.37 ppm: td; 3H; a hydrogen atom of a thiol group,
2.04 ppm: tt; 6H; a hydrogen atom attached to 9, 9 ′, 9 ″ carbon,
2.71 ppm: t; 6H; hydrogen atom attached to 10, 10 ′, 10 ″ carbon,
4.03 ppm: t; 6H; a hydrogen atom attached to 8, 8 ′, 8 ″ carbon,
6.79 ppm: d; 6H; hydrogen atom attached to the aromatic ring,
6.98 ppm: d; 6H; hydrogen atom attached to the aromatic ring.
[ ¹³ C-NMR]
A ¹³ C-NMR chart of TP-T1 is shown in FIG. ¹³ C-NMR was measured in deuterated chloroform using AL400 manufactured by JEOL.
21.0 ppm, 33.0 ppm: 9, 9 ′, 9 ″, 10, 10 ′, 10 ″ carbon atoms,
54.0 ppm: 1 carbon atom,
113.7 ppm, 129.7 ppm, 136.4 ppm: 2, 2 ′, 2 ″, 3, 3 ′, 3 ″, 4, 4 ′, 4 ″, 6, 6 ′, 6 ″, 7, 7 ', 7''carbon atoms,
156.6 ppm: 5, 5 ′, 5 ″ carbon atoms.

Example 2: Curing experiment of the polymerizable composition of the present invention A cured product was prepared by curing the composition of the polyfunctional thiol compound and the polyene compound of the present invention in the presence of a photopolymerization initiator, and examining its water resistance. did.
TP-T1 0.50 g and TMP3A (manufactured by Kyoeisha Chemical Co., Ltd., trimethylolpropane triacrylate, trade name “Light Acrylate TMPA”) 0.50 g and Irg184 (Ciba Specialty Chemicals Co., Ltd., trade name “Irgacure (Registered trademark) 184 ") 0.02 g was mixed and dissolved uniformly. This liquid was sandwiched between two fluorine-coated glass plates and irradiated with ultraviolet rays (3 J / cm ² ) with an ultrahigh pressure mercury lamp manufactured by Ushio Electric Co., Ltd., to produce a cured product having a thickness of 0.7 mm. This cured product was cut with a Comax laser processing machine (VD7050-15W) to prepare a test piece having a width of 10 mm and a length of 20 mm. The test piece was placed in water or a 5% by mass aqueous sodium hydroxide solution and immersed for 7 days at 23 ° C., and the mass before and after immersion was compared. The results are shown in Table 1.

Comparative Examples 1-2: Curing Experiment of Comparative Polymerizable Composition PE1 (Showa Denko Co., Ltd., pentaerythritol tetrakis (3-mercaptobutyrate), trade name “Karenz (registered trademark) PE1” instead of TP-T1 , Thiol group equivalent 139 g / eq) 0.50 g (Comparative Example 1) or 3-800 (manufactured by Cognis Japan Co., Ltd., trade name “Cap Cure (registered trademark) 3-800”, thiol group equivalent 278 g / eq) 0 A water / alkali resistance test was performed in the same manner as in Example 2 except that .50 g (Comparative Example 2) was used. The results are shown in Table 1.

Claims (13)

General formula (1)

(In the formula, R ¹ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³ represents a hydrogen atom. Or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group or alkoxy group having 1 to ⁴ carbon atoms, a is 0 or 1, b is 3 or 4, and c is 0 to 4 And a + b is 4.)
An aromatic ether-based polyfunctional primary thiol compound represented by   The aromatic ether polyfunctional primary thiol compound according to claim 1, wherein a = 1 and b = 3 in the general formula (1). The aromatic ether polyfunctional primary thiol compound according to claim 1, wherein, in the general formula (1), R ¹ is a linear or branched alkylene group having 1 or 2 carbon atoms in the main chain. The aromatic ether polyfunctional primary thiol compound according to claim 1, wherein, in the general formula (1), R ¹ is a methylene group, R ³ is a hydrogen atom or a methyl group, and c = 0.   The compound represented by the general formula (1) is tris (4- (3-mercaptopropoxy) phenyl) methane, 1,1,1-tris (4- (3-mercaptopropoxy) phenyl) ethane, or tetrakis (4 The aromatic ether polyfunctional primary thiol compound according to claim 1, which is-(3-mercaptopropoxy) phenyl) methane. General formula (1)

(In the formula, R ¹ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³ represents a hydrogen atom. Or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group or alkoxy group having 1 to ⁴ carbon atoms, a is 0 or 1, b is 3 or 4, and c is 0 to 4 And a + b is 4.)
A polymerizable composition comprising an aromatic ether-based polyfunctional primary thiol compound represented by formula (II) and a compound having an ethylenically unsaturated double bond.   The functional group having an ethylenically unsaturated double bond is at least one selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an allyl group, a vinyloxy group, and a styryl group. The polymerizable composition according to claim 6, wherein the compound having at least two of these functional groups.   The polymerizable composition according to claim 6 or 7, comprising a photopolymerization initiator.   The polymerizable composition according to any one of claims 6 to 8, comprising a polymerization inhibitor.   The polymerizable composition according to claim 6, comprising a secondary amine or a tertiary amine.   Hardened | cured material obtained by superposing | polymerizing the polymeric composition in any one of Claims 6-10. General formula (2)

(Wherein R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group or alkoxy group having 1 to ⁴ carbon atoms, a is 0 or 1, and b is 3 or 4 and c is an integer from 0 to 4 and a + b is 4.)
A polyhydric phenol compound represented by the general formula (3)

(In the formula, R ¹ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents a leaving group. Represents.)
Is reacted with a compound of the general formula (4)

(The symbols in the formula have the same meaning as defined in the formulas (2) and (3).)
Step 1 for obtaining a compound containing a terminal double bond represented by:
Step 2 of adding a mercapto group to the double bond site of the compound containing a terminal double bond
General formula (1), characterized in that

(The symbols in the formula have the same meaning as described above.)
The manufacturing method of the aromatic ether type polyfunctional primary thiol compound shown by these.   In the said General formula (3), X is a halogen or a sulfonate group, The manufacturing method of the aromatic ether type polyfunctional primary thiol compound of Claim 12.

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