CN103787887B

CN103787887B - The manufacture method of polybasic carboxylic acid and compositions, hardening resin composition, solidfied material and polybasic carboxylic acid

Info

Publication number: CN103787887B
Application number: CN201310712032.XA
Authority: CN
Inventors: 中西政隆; 洼木健; 洼木健一; 宫川直房; 川田义浩; 佐佐木智江; 青木静; 铃木瑞观; 枪田正人; 小柳敬夫
Original assignee: Nippon Kayaku Co Ltd
Current assignee: Nippon Kayaku Co Ltd
Priority date: 2009-06-22
Filing date: 2010-06-22
Publication date: 2016-06-22
Anticipated expiration: 2030-06-22
Also published as: CN102459144A; CN102459144B; TW201120000A; JP5713898B2; CN103787887A; TWI491590B; JPWO2010150524A1; KR101692450B1; KR20120030056A; WO2010150524A1

Abstract

The present invention relates to: the polycarboxylic acid compositions, the epoxy curing agent compositions comprising said composition that comprise the polybasic carboxylic acid represented by following formula (1), comprise this curing agent composition and the hardening resin composition of epoxy resin, its solidfied material and new polybasic carboxylic acid。Using this polybasic carboxylic acid and comprise the compositions of this polybasic carboxylic acid as the firming agent of epoxy resin use time, the volatilization of the firming agent when solidifying is few, the excellent optical characteristics of gained solidfied material, and heat durability is excellent。In following formula, R represents the alkyl of carbon number 1 to 6 independently of one another；P represents the divalent linking group defined by following (a): (a) linking group, its chain-like alkyl chain with branched structure being carbon number 6 to 20, this chain-like alkyl chain has the main chain of the straight chain of carbon number 3 to 6 and 2 to 4 side chains, and this side chain of at least two is the alkyl of carbon number 2 to 4。

Description

The manufacture method of polybasic carboxylic acid and compositions, hardening resin composition, solidfied material and polybasic carboxylic acid

To be on June 22nd, 2010, application number be 201080027952.2 (international application no is PCT/JP2010/004149) that the application is the applying date, denomination of invention are the divisional application of the application for a patent for invention of " manufacture method of polybasic carboxylic acid and compositions, hardening resin composition, solidfied material and polybasic carboxylic acid "。

Technical field

The present invention relates to and be particularly suitable for the polybasic carboxylic acid of electric and electronic material applications, polycarboxylic acid compositions and contain this polycarboxylic acid compositions curable epoxy resin composition as the firming agent of epoxy resin。Additionally, this polycarboxylic acid compositions is using other field of polybasic carboxylic acid, also serves as the raw material of coating, adhesive, products formed, quasiconductor, the sealing material use resin of photosemiconductor, the chip grafting material resin of photosemiconductor, polyimide resin etc. or modifying agent, plasticizer, crude lube stock, medicine pesticide intermediate product, the raw material of coating resin or resin for toner etc. useful。

Background technology

Polybasic carboxylic acid possesses high thermal stability, good electrical characteristic, excellent chemical-resistant and the sound response etc. when forming condensation body, premium properties as cross-linking agent, condensing agent etc.。Therefore, to manufacture raw material as macromolecule in recent years extremely noticeable and widely use for polybasic carboxylic acid。

Additionally, it is known that, polybasic carboxylic acid can also use as the firming agent of epoxy resin。

Containing the hardening resin composition of epoxy resin, as the resin of excellent heat resistance, build, the field such as building, automobile, aircraft uses。In recent years, the notebook computer etc. being particularly flooded with the mobile phone with photographing unit, ultrathin liquid crystal or plasma television, light weight in quasiconductor association area has with the electronic equipment of the high characteristic for key word light, thin, short, little。Accompany with this, in these quasiconductor association areas use material, be particularly representative with epoxy resin encapsulating material start the characteristic that requirement is very high。

It addition, in recent years, epoxy resin utilization in photoelectricity association area is attracted attention。Particularly with advanced IT application in recent years, in order to successfully transmit, process huge information, replace the conventional signal transmission undertaken by electric wiring, develop and pass on the technology of information with optical signal and be used。In the field of the opticses such as fiber waveguide, blue led and photosemiconductor that they use, for the curable resin wherein used, it is desirable to the solidfied material of the transparency and excellent durability can be provided。

It is said that in general, the firming agent of the epoxy resin used in such field can be enumerated: the compound of anhydrides。Use the anhydride formed by the polybasic carboxylic acid of annular aliphatic hydrocarbon especially and the solidfied material obtained, owing to resistance to optical activity is excellent, therefore this anhydride commonly used。Such as, the ester ring type anhydride such as methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabydrophthalic anhydride are generally used。Wherein, due to processing ease, therefore mainly using under room temperature is the methylhexahydrophthalic anhydride of liquid, methyl tetrahydrophthalic anhydride etc.。

But, individually using above-mentioned ester ring type anhydride as firming agent time, the part evaporation when solidifying owing to the vapour pressure of these firming agent is high, therefore has: the composition epoxy resin caused by the carboxylic acid anhydrides (firming agent) being absent from scheduled volume in solidfied material solidify bad problem and its characteristic significantly changes according to condition of cure thus the problem that is difficult to obtain having the solidfied material of stable objects performance。It addition, a large amount of when producing solidfied material in open system, these firming agent evaporate in air, thus also generating the problem that: harmful substance discharge into the atmosphere cause environmental pollution, pollution etc. to the harmful effect of human body and production line。

Additionally, the solidfied material using conventional firming agent and obtain, when sealing LED, particularly SMD (SurfaceMountDevice: surface mounted component), make consumption few due to resin, therefore produce following problems: impact that is bad and that cannot obtain stability is notable in above-mentioned solidifying, cause distribution to expose due to the generation etc. of pit or make sealing not exclusively, produce when Reflow Soldering to break and/or stripping etc., make the problems such as quality deterioration due to long-term bright light。

On the other hand, approximate with the polybasic carboxylic acid of present invention polybasic carboxylic acid, it is known that for purposes such as emulsifying agents in patent documentation 4 and 5 etc.。

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2003-277473 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2008-063333 publication

Patent documentation 3: No. 2813028 publications of Japan Patent

Patent documentation 4: No. 2915962 publications of Japan Patent

Patent documentation 5: Japanese Unexamined Patent Publication 3-26743 publication

Summary of the invention

It is an object of the invention to provide: during solidification the volatilization of firming agent less and solidfied material can realize the firming agent of stable target capabilities, firming agent use new polybasic carboxylic acid, the composition epoxy resin (hardening resin composition) comprising this polybasic carboxylic acid or curing agent composition and this composition epoxy resin (hardening resin composition) solidfied material。And, it is provided that for realizing the useful new polybasic carboxylic acid of the object of the invention and the compositions comprising this polybasic carboxylic acid。Particularly, it is an object of the invention to provide: the heat-resistant quality of solidfied material, specifically, the hardening resin composition of the excellent optical characteristics such as the illumination conservation rate in the conservation rate of the absorbance of light, LED, and for realizing this target polybasic carboxylic acid and the polycarboxylic acid compositions comprising this polybasic carboxylic acid。

The present inventor has carried out research extensively and profoundly in view of above-mentioned present situation, and result completes the present invention。

That is, the present invention relates to following invention。

1. a polycarboxylic acid compositions, it comprises the polybasic carboxylic acid represented by following formula (1),

In formula, R represents hydrogen atom, the alkyl of carbon number 1 to 6 or carboxyl independently of one another；P represents the divalent linking group defined by following (a) or (b):

A () linking group, it is the chain-like alkyl chain with branched structure of carbon number 6 to 20, and this chain-like alkyl chain has the main chain of the straight chain of carbon number 3 to 12 and 2 to 4 side chains, and the carbon number of at least one this side chain is 2 to 10；

(b) divalent linking group, its for from be selected from can have on ring methyl, Tricyclodecane Dimethanol or the pentacyclopentadecane dimethanol multi-ring glycol of at least one bridging removes 2 hydroxyls after the group that obtains,

But, when P is (b), R represents the group beyond hydrogen atom。

2. the polycarboxylic acid compositions as described in above-mentioned 1, wherein, divalent linking group is the linking group defined by (a), and the linking group defined by (a) is any one in the divalent group represented by following formula (a1),

Formula (a1):

In formula, the * mark of the end of each group represents at * mark place and adjacent oxygen atoms bond。

3. the polycarboxylic acid compositions as described in above-mentioned 1 or 2, wherein, in the linking group of (a), main chain is the straight chain of carbon number 3 to 6, and at least 2 side chains are the alkyl of carbon number 2 to 4。

4. such as the polycarboxylic acid compositions according to any one of above-mentioned 1 to 3, wherein, (a) linking group defined is the divalent group obtained after removing 2 hydroxyls from 2,4-diethyl-1,5-PD。

5. the polycarboxylic acid compositions as described in above-mentioned 1, wherein, divalent linking group is the linking group defined by (b), and the linking group defined by (b) is any one in the divalent group represented by following formula (b1),

Formula (b1):

In formula, the multiple R existed in each structural formula²Represent hydrogen atom or methyl independently of one another。

6. such as the polycarboxylic acid compositions according to any one of above-mentioned 1 to 5, it is characterised in that comprise R²It is the polybasic carboxylic acid of hydrogen atom。

7. such as the polycarboxylic acid compositions according to any one of above-mentioned 1 to 6, it is characterised in that comprise the polybasic carboxylic acid that R is methyl and/or carboxyl in the formula (1) of 50 moles of more than %。

8., such as the polycarboxylic acid compositions according to any one of above-mentioned 1 to 7, wherein, the R in formula (1) is methyl or carboxyl。

9. the polycarboxylic acid compositions as described in above-mentioned 8, wherein, the group beyond hydrogen atom is methyl。

10. such as polycarboxylic acid compositions according to any one of above-mentioned 1 to 8, wherein, polycarboxylic acid compositions comprises: polybasic carboxylic acid that at least one is represented by formula (1) and can by methyl substituted C₄To C₇Ring-type two, three or tetracarboxylic anhydride。

11. the polycarboxylic acid compositions as described in above-mentioned 10, wherein it is possible to by methyl substituted C₄To C₇Ring-type two, three or tetracarboxylic anhydride, for can by methyl substituted hexamethylene two or tricarboxylic acid anhydride。

12. a hardener for epoxy resin, the polycarboxylic acid compositions described in the polybasic carboxylic acid of its contained (1) or above-mentioned 10 or 11。

13. the hardener for epoxy resin as described in above-mentioned 12, it is for comprising:

Polybasic carboxylic acid, wherein, the divalent linking group represented by P in formula (1) is the linking group defined by (a), and the linking group defined by (a) is the divalent group described in following (1), and

Anhydride, it is at least one in the group of the anhydride composition described in choosing freely following (2),

Polycarboxylic acid compositions,

(1) divalent group:

The divalent group obtained after removing 2 hydroxyls from 2,4-diethyl-1,5-pentanediol；

(2) anhydride:

Methylhexahydrophthalic anhydride and hexamethylene-1,2,4-tricarboxylic acids-1,2-acid anhydride。

14. the hardener for epoxy resin as described in above-mentioned 12, it is for comprising:

Polybasic carboxylic acid, wherein, the divalent linking group represented by P in formula (1) is the linking group defined by (b), and the linking group defined by (b) is any one in the divalent group represented by formula (b1) described in following (1), and

Anhydride, it is at least one in the group that the anhydride described in choosing freely following (2) is constituted, polycarboxylic acid compositions,

(1) formula (b1):

In formula, the multiple R existed in each structural formula²Represent hydrogen atom or methyl independently of one another；

(2) anhydride:

15. a hardening resin composition, it comprises the curing agent composition according to any one of polybasic carboxylic acid or above-mentioned 12 to 14 of the formula (1) according to any one of above-mentioned 1 to 7 and epoxy resin。

16. the hardening resin composition as described in above-mentioned 15, wherein, epoxy resin is alicyclic epoxy resin。

17. the hardening resin composition as described in above-mentioned 16, wherein, curing agent composition is the curing agent composition described in above-mentioned 13。

18. the hardening resin composition as described in above-mentioned 16, wherein, curing agent composition is the curing agent composition described in above-mentioned 14。

19. a solidfied material, it is the solidfied material of the hardening resin composition described in above-mentioned 15。

20. a manufacture method for the polybasic carboxylic acid represented by formula (1) described in above-mentioned 1, wherein, make dihydroxylic alcohols and (c) reaction of following (a) or (b),

A the chain fatty race dihydroxylic alcohols with branched structure of () carbon number 6 to 20, wherein, chain-like alkyl chain has the main chain of the straight chain of carbon number 3 to 12 and 2 to 4 side chains, and at least 1 this side chain is the alkyl of carbon number 2 to 10；

B the multi-ring glycol of () bridging, it is for selected from having at least one methyl, Tricyclodecane Dimethanol or pentacyclopentadecane dimethanol on ring；

(c) anhydride, it is for selecting free hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and hexamethylene-1,2, at least one anhydride in the group that 4-tricarboxylic acid anhydride is constituted, but, when (b), it is for comprising methylhexahydrophthalic anhydride or hexamethylene-1, the at least one anhydride of any one in 2,4-tricarboxylic acid anhydrides。

21. the manufacture method of the polybasic carboxylic acid as described in above-mentioned 20, wherein, it is calculated as the ratio of 0.001 to 2 equivalent relative to anhydride group 1 equivalent with the hydroxyl equivalent of dihydroxylic alcohols, at reaction temperature 40 to 150 DEG C, makes the dihydroxylic alcohols of (a) or (b) and the anhydride reaction of (c)。

22. the manufacture method of the polybasic carboxylic acid as described in above-mentioned 21, wherein, the anhydride of (c) is the mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride。

23. the manufacture method of the polybasic carboxylic acid as described in above-mentioned 21 or 22, wherein, dihydroxylic alcohols is 2,4-diethyl-1,5-PD or 2-ethyl-2-butyl-1,3-PD。

24. the manufacture method of the polybasic carboxylic acid as described in above-mentioned 21, it includes the step making 2,4-diethyl-1,5-PD and methylhexahydrophthalic anhydride react。

25. the manufacture method of the polybasic carboxylic acid as described in above-mentioned 21, it includes the step making to react with methylhexahydrophthalic anhydride without the Tricyclodecane Dimethanol replaced or pentacyclopentadecane dimethanol。

26. the polybasic carboxylic acid represented by following formula (1),

A () linking group, it is the chain-like alkyl chain with branched structure of carbon number 6 to 20, and this chain-like alkyl chain has the main chain of the straight chain of carbon number 3 to 12 and 2 to 4 side chains, and the carbon number of at least one this side chain is 2 to 10；Or

But, when P is (b), R represents the group beyond hydrogen atom。

27. the polybasic carboxylic acid as described in above-mentioned 26, wherein, P serves as reasons the divalent linking group that (a) defines, and is the linking group that carbon number is 2 to 10 of at least 2 side chains。

28. the polybasic carboxylic acid as described in above-mentioned 27, wherein, (a) the divalent linking group defined is the alkylidene obtained after removing 2 hydroxyls from 2,4-diethyl-1,5-PD。

29. the polybasic carboxylic acid as described in above-mentioned 26, wherein, P serves as reasons the divalent linking group that (b) defines。

30. the polybasic carboxylic acid as described in above-mentioned 26, wherein, the R in formula (1) is methyl or carboxyl。

Invention effect

The polybasic carboxylic acid of the formula (1) of the present invention or polycarboxylic acid compositions, have the ability to cure of excellent epoxy resin, and the firming agent as epoxy resin is useful。And this polybasic carboxylic acid coordinated in the epoxy or this polycarboxylic acid compositions, make the volatilization in the temperature range of epoxy resin cure few being generally used for。As a result, processing ease can stably realize the target capabilities of solidfied material。Specifically, it is possible to obtain the epoxy resin cured product that transparency is high and heat durability is excellent。This heat durability particularly can be enumerated such as: reflux-resisting welded property, light the heat durability of the optical characteristics such as absorbance conservation rate and LED illumination conservation rate under long-term bright light。

Detailed description of the invention

The polybasic carboxylic acid of the present invention is the polybasic carboxylic acid represented by following formula (1), and the polycarboxylic acid compositions of the present invention is characterised by: comprise the polybasic carboxylic acid represented by following formula (1),

(b) divalent linking group, its for from be selected from can have on ring methyl, Tricyclodecane Dimethanol or the pentacyclopentadecane dimethanol multi-ring glycol of at least one bridging removes 2 hydroxyls after the group that obtains。

More specifically, the compound that the polybasic carboxylic acid of the present invention is represented by formula (1), at least 1 R is methyl or carboxyl, particularly more preferably 2 R are the compound of methyl or carboxyl。

The polycarboxylic acid compositions of the present invention, the compositions comprising at least 2 kinds of compounds represented by above formula (1), or comprise compound that at least one represents by above formula (1) and have saturated structures anhydride, preferably can by methyl substituted C₄To C₇Ring-type two, three or tetracarboxylic anhydride, more preferably can by methyl substituted C₄To C₇The compositions of ring-type two or tricarboxylic acid anhydride。

In described formula (1), P the linking group represented is the divalent linking group defined by above-mentioned (a) or (b), below they is specifically described。

The divalent linking group defined by above-mentioned (a), being the divalent chain-like alkyl chain obtained after removing hydroxyl the alcohol (dihydroxylic alcohols) of the divalent with branched structure from carbon number 6 to 20, its structure having is for main chain and to have the alkyl chain (being called side chain) after this alkyl chain branch with the alkyl chain clamped by the 2 of dihydroxylic alcohols alcoholic extract hydroxyl groups。This side chain from any carbon atom branch constituting main chain, also can comprise such as: from the situation of carbon atom (terminal carbon of the main chain) branch that alcoholic extract hydroxyl group is bonded。As long as have the linking group of this structure, then can being any linking group, the particular instantiation of such linking group be in following formula (a1)。

Formula (a1)

In described formula, the oxygen atoms bond of the both sides of the P in * mark place with formula (1)。

The alkylidene linking group defined by above-mentioned (a), as long as the structure relative to main chain alkylidene with alkyl branches (side chain) is then not particularly limited, preferred main chain is carbon number to be the main chain of more than 3 and has the linking group of at least 1 alkyl side chain, it is particularly preferred to main chain is carbon number to be the main chain of more than 3 and have the linking group of more than 2 alkyl side chains。Can enumerate such as preferred linking group: there are the main chain of the straight chain of carbon number 3 to 12 and 2 to 4 side chains, and the carbon number of at least one this side chain is 2 to 10。Now, it is preferred that the carbon number of at least two side chain is 2 to 10。

As the linking group defined by above-mentioned (b), it is possible to enumerate the divalent group represented by following formula (b1)。

Formula (b1):

Wherein, it is preferable that R²It is the linking group of hydrogen atom。

The polybasic carboxylic acid represented by formula (1) of the present invention, it is possible to by making corresponding for P diatomic alcohol compounds with above formula (1) and can by C₁To C₆The hexahydrophthalic anhydride that the preferred methyl of alkyl or carboxyl replace carries out additive reaction and obtains。

It addition, the polycarboxylic acid compositions of the present invention can be obtained by following method for making。

In the present invention, as obtaining the method that comprises the polycarboxylic acid compositions of at least 2 kinds of polybasic carboxylic acids represented by above formula (1), there is following method: the method being undertaken mixing by the single polybasic carboxylic acid represented by formula (1) that at least 2 kinds are obtained by said method；Or, when synthesizing the above-mentioned polybasic carboxylic acid represented by formula (1), the mixture using at least 2 kinds as above-mentioned hexahydrophthalic anhydride or the method using 2 kinds of above-mentioned dihydroxylic alcohols to carry out additive reaction。

It addition, in the present invention, as obtaining comprising polybasic carboxylic acid that at least one represents and can by methyl substituted C by above formula (1)₄To C₇The method of the polycarboxylic acid compositions of both ring-type two, three or tetracarboxylic anhydride, it is possible to enumerate following method。

(1) the single polybasic carboxylic acid represented by formula (1) that at least one obtained by said method and can by methyl substituted C₄To C₇The method that ring-type two, three or tetracarboxylic anhydride carry out mixing；Or

(2) when the polybasic carboxylic acid that synthesis is represented by formula (1), the hexahydrophthalic anhydride that can be replaced by methyl or carboxyl used as one of raw material is excessively used, in reactant liquor after the reaction, formula (1) method of the polybasic carboxylic acid represented and the above-mentioned phthalic anhydride Coexistence mode as raw material use。

As the above-mentioned anhydride used in the synthesis of the polybasic carboxylic acid represented by formula (1), adducible polybasic acid anhydride is: have cyclohexane structure, this cyclohexane ring there are methyl substituted or carboxyl replace or without replacement, and the anhydride group being bonded with cyclohexane ring has more than 1 (preferably 1) in molecule。Specifically, it is possible to enumerate such as: 1,2,4-cyclohexanetricarboxylic acid-1,2-acid anhydride, 4-hexahydrotoluene-1,2-dicarboxylic anhydride or hexamethylene-1,2-dicarboxylic anhydride etc.。

In order to obtain the single compound of the polybasic carboxylic acid represented by formula (1), it is possible to use any one in above-mentioned anhydride reacts。

It addition, for the polycarboxylic acid compositions obtaining the present invention, as mentioned above, at least 2 kinds that use these carboxylic acid anhydrides react, or preferably: relative to described dihydroxylic alcohols, at least one being excessively used these carboxylic acids reacts, thus containing the mode of anhydride when reacting end in reactant liquor。

When at least using 2 kinds of these anhydride, it is possible to be arbitrary 2 kinds, in the present invention, consider from optical characteristics, it is preferable that C₁To C₆The preferred methyl of alkyl is or/and the hexahydrophthalic anhydride that replaces of carboxyl, it is preferable that without the hexahydrophthalic anhydride replaced at most less than 50 weight %, it is preferable that below 40 weight %, more preferably below 35 weight %, it is preferred that below 30 weight %。

In this manual, below, % is without being particularly limited to then for weight %。

When at least using 2 kinds of anhydride, methyl substituted is or/and the hexahydrophthalic anhydride that replaces of carboxyl is in whole anhydride, it is preferred to more than 65%, more preferably more than 85%, it is particularly preferred to more than 90%。

As the above-mentioned raw materials dihydroxylic alcohols used in the synthesis of the polybasic carboxylic acid represented by formula (1), it is possible to enumerate two ends at linking group P with the dihydroxylic alcohols of hydroxyl。

Specifically, it is the dihydroxylic alcohols of the chain-like alkyl chain with branched structure in the linking group defined by (a) with total carbon atom number 6 to 20。More specifically, it is possible to the dihydroxylic alcohols enumerated is: two ends at the main chain of carbon number 3 to 12 have hydroxyl, this main chain has 2 to 4 side chains, and the carbon number of at least 1 this side chain (preferably at least 2) is 2 to 10。

As compound more specifically, it is possible to enumerate: the position of the * mark in the linking group described in described formula (a1) is bonded with the compound of hydroxyl。

In the dihydroxylic alcohols used as raw material, it is preferred that dihydroxylic alcohols is: at least there is the side chain that at least 2 is carbon number 2 to 4 in 2 side chains and this side chain。

In such skeleton, can enumerate as particularly preferred dihydroxylic alcohols: 2,4-diethyl-1,5-PD, 2-ethyl-2-butyl-1,3-PD, 2-ethyl-1,3-hexanediol etc., it is particularly preferred to 2,4-diethyl-1,5-PD。

It addition, the multi-ring glycol of bridging during as the linking group defined by described (b) in formula (1), it is using tristane structure, pentacyclopentadecandimethanol structure as the glycols of main skeleton, following formula (b2) represents。

In formula, R²Exist multiple, represent hydrogen atom or methyl independently of one another。

Specifically, it is possible to enumerate: Tricyclodecane Dimethanol, methyl Tricyclodecane Dimethanol, pentacyclopentadecane dimethanol etc.。

Reaction as anhydride Yu dihydroxylic alcohols, it is however generally that be using acid or alkali as the additive reaction of catalyst, but, the reaction carried out when in the present invention particularly preferably in catalyst-free。

When using catalyst, as operable catalyst, it is possible to enumerate such as: acid compounds such as hydrochloric acid, sulphuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-methyl benzenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acids；The metal hydroxidess such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide；The amines such as triethylamine, tripropyl amine (TPA), tri-n-butylamine；The hetero ring type compounds such as pyridine, dimethylamino naphthyridine, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene, imidazoles, triazole, tetrazolium；The quaternary ammonium salts etc. such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, trimethylethyl ammonium hydroxide, thmethylpropyl ammonium hydroxide, trimethyl butyl ammonium hydroxide, trimethyl cetyl ammonium hydroxide, tricaprylmethyl ammonium hydroxide, tetramethyl ammonium chloride, 4 bromide, tetramethyl-ammonium iodide, tetramethyl ammonium acetate, tricaprylmethyl ammonium acetate。These catalyst can use a kind or two or more mixing be used。Wherein, it is preferable that triethylamine, pyridine, dimethylamino naphthyridine。

The consumption that makes of catalyst is not particularly limited, and relative to total amount 100 weight portion of raw material, uses 0.001 to 5 weight portion to be preferred generally according to needs。

In this reaction, it is preferable that react under condition of no solvent, but organic solvent can also be used。Organic solvent make consumption, relative to the total amount 1 part of described anhydride and described dihydroxylic alcohols as reaction substrate, with mass ratio range for 0.005 to 1 part, it is preferable that 0.005 to 0.7 part, more preferably 0.005 to 0.5 part (i.e. below 50 weight %)。Organic solvent make consumption relative to above-mentioned reaction substrate 1 weight portion with mass ratio range more than 1 part time, owing to the carrying out of reaction becomes extremely slow, therefore not preferred。Concrete example as operable organic solvent, it is possible to use: the alkanes such as hexane, hexamethylene, heptane；The aromatic hydrocarbon compound such as toluene, dimethylbenzene；The ketones such as butanone, methylisobutylketone, Ketocyclopentane, Ketohexamethylene；The ethers such as ether, oxolane, dioxane；The ester compounds etc. such as ethyl acetate, butyl acetate, methyl formate。

Even if this reaction can also be sufficiently carried out reaction at the temperature of about 20 DEG C。From the viewpoint of the response time, reaction temperature preferably 30 to 200 DEG C, more preferably 40 to 200 DEG C, it is particularly preferred to 40 to 150 DEG C。When particularly carrying out this reaction under condition of no solvent, with the volatilization of anhydride, it is thus preferred to the reaction of less than 100 DEG C, it is particularly preferred to the reaction of 30 to 100 DEG C or 40 to 100 DEG C。

The reactive ratio of described anhydride and described dihydroxylic alcohols, in theory preferably in etc. reaction under molar conditions, but can change as required。Namely, as described below, in the polycarboxylic acid compositions of the present invention used in the hardener for epoxy resin compositions as the present invention, when the compositions of the polybasic carboxylic acid of contained (1) that uses as the firming agent of liquid and described anhydride, the anhydride particularly used in the synthesis of the polybasic carboxylic acid of formula (1) is identical with the anhydride coordinated in this polycarboxylic acid compositions, during fabrication, the described anhydride excessive relative to described dihydroxylic alcohols reacts, when the reaction of this anhydride with this dihydroxylic alcohols terminates, the mixture (curing agent composition of liquid) of this anhydride and the polybasic carboxylic acid of described formula (1) can be obtained。

The interpolation ratio of the two concrete when reacting is, in their functional equivalent, relative to this anhydride group 1 equivalent, in the hydroxyl equivalent of this dihydroxylic alcohols preferably 0.001 to 2 equivalent, more preferably 0.01 to 1.5 equivalent, it is preferred that the ratio of 0.01 to 1.1 equivalent adds this dihydroxylic alcohols。During curing agent composition fabricated as described above, in the hydroxyl equivalent of this dihydroxylic alcohols, generally in the scope of 0.01 to 0.7 equivalent, preferably 0.01 to 0.5 equivalent, use this dihydroxylic alcohols。

Response time is different also according to reaction temperature, catalytic amount etc., considers from industrial viewpoint, and long reaction can consume great energy, therefore not preferred。It addition, the too short response time means its reaction sharply, consider not preferred from a security point。Preferably range for about 1 to about 48 hour, it is preferable that about 1 to about 36 hour, more preferably from about 1 to about 24 hour, it is preferred that about 2 to about 10 hours。

After reaction terminates, when using catalyst, remove catalyst via neutralization, washing, absorption etc. respectively, and remove solvent by distilling and obtain target polybasic carboxylic acid。It addition, in the reaction of catalyst-free, it is possible to solvent is removed in distillation as required, it addition, when solvent-free, catalyst-free, product can be directly taken out and obtains goods。

As optimal manufacture method, it is under catalyst-free, solvent-free condition, at 40 to 150 DEG C, make described anhydride, described diol reaction, after reaction terminates, the method directly taking out product。

The polybasic carboxylic acid represented by described formula (1) so obtained or the compositions comprising this polybasic carboxylic acid, it is common that present resin-like or the liquid (sometimes crystallization) of colourless to flaxen solid-state。

Generally, when the linking group P in formula (1) is the alkylidene with side chain defined by (a), the resin-like of colourless to flaxen solid-state is presented。When linking group P in formula (1) is the divalent linking group obtained after removing hydroxyl from the multi-ring glycol of the bridging defined by (a), and be the linking group defined by (a) and when reacting in excessive anhydride, the shape of reaction product typically exhibits liquid。

When linking group P in formula (1) is the linking group defined by (b), substituent R is the polybasic carboxylic acid of hydrogen atom and can see when solidifying painted, in particularly severe optical applications and improper。When the compound that R is methyl or carboxyl, such painted few, its optical characteristics improves。

In the compound with the linking group defined by (a) of above formula (1), when the compound that R is methyl or carboxyl, its optical characteristics improves, it is thus preferred to。

That is, as the polycarboxylic acid compositions of the present invention, it is preferred that compositions comprises: preferably R has methyl or carboxyl or the polybasic carboxylic acid of the formula of the two (1)。When polycarboxylic acid compositions comprises two or more this polybasic carboxylic acid, total amount relative to polybasic carboxylic acid, it is preferable that comprise 50 moles of more than % at least R for the compositions of the polybasic carboxylic acid polybasic carboxylic acid of the preferred methyl of described alkyl or carboxyl (R be) of the formula (1) of hydrogen atom。More preferably 70 moles of more than %, most preferably 90 moles of more than % R are comprised not for the polycarboxylic acid compositions of the polybasic carboxylic acid of the formula (1) of hydrogen atom。All the other are R is the polybasic carboxylic acid of formula (1) of hydrogen atom。

The polybasic carboxylic acid represented by formula (1) of the present invention, preferred R is the group beyond hydrogen atom, more preferably R is the polybasic carboxylic acid of methyl or carboxyl, or comprise the polycarboxylic acid compositions of the present invention of this polybasic carboxylic acid, its excellent transparency, firming agent as epoxy resin, coating, adhesive, products formed, quasiconductor, the sealing material use resin of photosemiconductor, the chip grafting material resin of photosemiconductor, polyamide, the raw material of polyimide resin etc. or modifying agent, plasticizer and crude lube stock, medicine pesticide intermediate product, the raw material of coating resin, resin for toner is useful。Particularly using the polycarboxylic acid compositions of the present invention as epoxy resin firming agent use time, curing performance is excellent, and the transparency of its solidfied material is excellent。Therefore, the polycarboxylic acid compositions of the present invention be extremely suitable in the sealing of the White LED as high brightness and other photosemiconductor use hardener for epoxy resin。

The polycarboxylic acid compositions of the polybasic carboxylic acid of contained (1) time hereinafter, for using as LCM in the polycarboxylic acid compositions of the present invention and the present invention of anhydride illustrates。

This polycarboxylic acid compositions preferred, the polybasic carboxylic acid of contained (1) and can by methyl substituted C₄To C₇Ring-type two, three or tetracarboxylic anhydride, the ratio of the two is, relative to polybasic carboxylic acid 1 weight portion of formula (1), the ratio of this anhydride is 0.1 to 10 weight portion, it is preferable that 0.5 to 8 weight portion, more preferably 1 to 8 weight portion。

In this polycarboxylic acid compositions, when contained above-mentioned anhydride is identical with the anhydride used when the polybasic carboxylic acid of the formula of manufacture (1), then described above, when the polybasic carboxylic acid of the formula of manufacture (1), by manufacturing as the anhydride that raw material uses relative to being excessively used in the way of reaching above-mentioned scope as the dihydroxylic alcohols that raw material uses by the anhydride of residual after making reaction, the reactant liquor thus obtained can use directly as the polycarboxylic acid compositions of the present invention, it is thus preferred to。

Other manufacture method as this polycarboxylic acid compositions, it is possible to by by the polybasic carboxylic acid of formula obtained above (1) with above-mentioned can by methyl substituted C₄To C₇Ring-type two, three or tetracarboxylic anhydride dissolve be obtained by mixing with above-mentioned ratio uniform。

Polybasic carboxylic acid as formula (1) contained in this polycarboxylic acid compositions, it is possible to be a kind, it is also possible to be of more than two kinds multiple。When the polybasic carboxylic acid of contained formula (1) is a kind, the polybasic carboxylic acid of formula (1) is as described above, it is preferred to compound that R is methyl or carboxyl。It addition, when comprising the polybasic carboxylic acid of multiple formula (1), relative to the total amount of this polybasic carboxylic acid, the polybasic carboxylic acid that R is methyl or carboxyl in formula (1) preferably comprises 50 moles of more than %, more preferably 65 moles of more than %。

As above-mentioned can by methyl substituted C₄To C₇Ring-type two, three or tetracarboxylic anhydride, as long as C₄To C₇Ring has 2 to 4, the anhydride of the preferred polybasic carboxylic acid of 2 to 3 carboxyls, is then not particularly limited。Specifically, it is possible to enumerate: hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic anhydride, dicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, methyl bicycle [2.2.1] heptane-2,3-dicarboxylic anhydride, hexamethylene-1,2,4-tricarboxylic acids-1,2-acid anhydride etc.。The cyclohexane dicarboxylic acid acid anhydride (hexahydrophthalic anhydride that can be replaced by methyl or carboxyl) that preferably can be replaced by methyl or carboxyl。Example as them, it is possible to enumerate such as: hexahydrophthalic anhydride, methylhexahydrophthalic anhydride or hexamethylene-1,2,4-tricarboxylic acids-1,2-acid anhydride etc.。

In this polycarboxylic acid compositions, the preferred proportion shared by polybasic carboxylic acid of formula (1), relative to the gross weight of described anhydride Yu this polybasic carboxylic acid, is 20 to 80 weight %, more preferably 30 to 75 weight %。

Hereinafter, the hardener for epoxy resin for the present invention illustrates。

The hardener for epoxy resin of the present invention is the polybasic carboxylic acid of contained (1) or the firming agent comprising this polybasic carboxylic acid and anhydride。Preferred polybasic carboxylic acid as formula (1), it is possible to enumerate: R is the polybasic carboxylic acid beyond hydrogen atom, and more preferably R is the polybasic carboxylic acid of methyl or carboxyl, and particularly all of R is the polybasic carboxylic acid of methyl or carboxyl。

Using the polybasic carboxylic acid of formula (1) firming agent as epoxy resin, when using especially as LCM, it is preferable that the anhydride of mixes liquid is as the polycarboxylic acid compositions of the present invention of liquid。The compositions of this liquid can be suitable as the hardener for epoxy resin compositions of the present invention and use。Anhydride as operable liquid, it is preferable that not there is aromatic rings in its structure and there is the anhydride of saturated rings structure。Specifically, it is possible to for anhydride cited in the polycarboxylic acid compositions explanation of the invention described above。It addition, mixing ratios etc. are it is also preferred that the illustrated scope that exists together。Therefore, the polycarboxylic acid compositions of the present invention of above-mentioned contained (1) polybasic carboxylic acid and anhydride, it is possible to the hardener for epoxy resin compositions directly as the present invention uses。

In this firming agent, it is also possible to comprise following described curing catalysts, additive, inorganic filling material etc. simultaneously。

The hardening resin composition of the present invention of the hardener for epoxy resin of the polybasic carboxylic acid having contained (1) set forth below or the present invention。

The hardening resin composition of the present invention comprises the epoxy resin as neccessary composition。

As the epoxy resin that can use in the hardening resin composition of the present invention, it is possible to enumerate: phenolic resin varnish type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, tritan. type epoxy resin, phenol aralkyl type epoxy resin etc.。Specifically, can enumerate: bisphenol-A, bisphenol S, sulfur diphenol, bis-phenol, terpene diphenol, 4, 4'-bis-phenol, 2, 2'-bis-phenol, 3, 3', 5, 5'-tetramethyl-[1, 1'-xenyl]-4, 4'-glycol, hydroquinone, resorcinol, naphthalene glycol, three (4-hydroxyphenyl) methane, 1, 1, 2, 2-tetra-(4-hydroxyphenyl) ethane, phenols (phenol, the phenol that alkyl replaces, naphthols, the naphthols that alkyl replaces, dihydroxy benzenes, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, benzaldehyde, hydroxy benzaldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, bran aldehyde, 4, 4'-bis-(chloromethyl)-1, 1'-biphenyl, 4, 4'-bis-(methoxy)-1, 1'-biphenyl, 1, 4-bis-(chloromethyl) benzene, 1, the condensation polymer of 4-bis-(methoxy) benzene etc. and their modifier；The halogenated bisphenols class of tetrabromobisphenol A etc., the glycidyl ether compound derived by alcohols；Alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, silsesquioxane alkanes epoxy resin (in chain, ring-type, scalariform, or the siloxane structure of the mixed structure at least of more than two kinds in them has glycidyl and/or the epoxy resin of epoxycyclohexyethylSiOi alkyl structure) etc. the epoxy resin of solid-state or liquid, but be not restricted to that these。

When particularly the hardening resin composition of the present invention being used for optical applications, as epoxy resin, preferred alicyclic epoxy resin is or/and contain the polyorganosiloxane resin (epoxy resin of preferred silsesquioxane alkyl structure) of epoxy radicals, it is particularly preferred to combination uses。When being particularly alicyclic epoxy resin, it is preferable that skeleton has the compound of epoxycyclohexyethylSiOi alkyl structure, it is particularly preferred to by having the epoxy resin that the oxidation reaction of the compound of cyclohexene obtains。

As these alicyclic epoxy resins, can enumerate: will can pass through the esterification (Tetrahedron the 36th volume the 2409th page (1980) of the cyclohexene carboxylate esterification with alcohols or cyclohexene methanol and carboxylic acids, the method that TetrahedronLetter the 4475th page (1980) etc. are described), or the Tischenko reaction of hexamethylene olefine aldehydr (Tischenkoreaction) (Japanese Unexamined Patent Publication 2003-170059 publication, the method that Japanese Unexamined Patent Publication 2004-262871 publication etc. are described), and the product etc. that the compound that manufactures of the ester exchange reaction of cyclohexene carboxylate ester (Japanese Unexamined Patent Publication 2006-052187 publication etc. described methods) carries out aoxidizing and obtains。

As alcohols, as long as have the compound of alcoholic extract hydroxyl group, then it is not particularly limited, it is possible to enumerate: the glycolss such as ethylene glycol, propylene glycol, 1,3-PD, 1,2-butanediol, BDO, 1,5-PD, 1,6-hexanediol, cyclohexanedimethanol；Three alcohols such as glycerol, trimethylolethane, trimethylolpropane, tri hydroxy methyl butane, 2-methylol 1,4-butanediol；Tetramethylolmethane etc. four alcohols etc.。It addition, as carboxylic acids, it is possible to enumerate: succinic acid, maleic acid, fumaric acid, phthalic acid, M-phthalic acid, adipic acid, cyclohexane dicarboxylic acid etc., but be not restricted to that these。

Furthermore it is possible to enumerate the acetal compound that cyclohexene aldehyde derivatives is obtained by aldolisation with alcohol。As reaction method, it is possible to by applying general acetalation manufacture, for instance disclosed: use toluene, dimethylbenzene equal solvent as reaction medium, azeotropic dehydration, while the method reacted (No. 2945008 publications of U.S. Patent No.)；After polyhydric alcohol is dissolved in concentrated hydrochloric acid, it is slowly added into aldehydes, while the method reacted (Japanese Laid-Open Patent Publication 48-96590 publication)；Use water as the method (No. 3092640 publications of U.S. Patent No.) of reaction medium；Use organic solvent as the method (Japanese Unexamined Patent Publication 7-215979 publication) of reaction medium；Use the method (Japanese Unexamined Patent Publication 2007-230992 publication) etc. of solid acid catalyst。Consider from the stability of structure, it is preferable that cyclic acetal structure。

Furthermore it is possible to enumerate: the product etc. that the ester ring type multiolefin oxidations such as VCH or limonene, dicyclopentadiene, three cyclopentadiene, methyl dicyclopentadiene, dicyclohexene, octadiene are obtained。

Concrete example as these epoxy resin, can enumerate: ERL-4221, ERL-4299 (are all trade name, be DowChemical manufacture), EPOLEADGT401, EHPE3150, EHPE3150CE (be all trade name, it is Daicelchemical industrial group to manufacture) and dicyclopentadiene diepoxide etc., but be not restricted to that these (list of references: エ Port キシ fat (epoxy resin introduction) basis section I 76-85 pages)。They can be used alone and also can two or more combination be used。

As preferred alicyclic epoxy resin, it is preferable that can have the expoxycyclohexyl of methyl such as with-COO-CH₂-、-COO-(C₃To C₈Divalent representative examples of saturated aliphatic base)-COO-,-CH₂-COO-(C₃To C₈Divalent representative examples of saturated aliphatic base)-COO-or-CH₂-COO-(C₃To C₈Divalent representative examples of saturated aliphatic base)-COO-CH₂-wait the difunctional epoxy resin that linking group is bonded。

As the polyorganosiloxane resin containing epoxy radicals, it is preferable that the epoxy resin of silsesquioxane alkyl structure。Epoxy resin as silsesquioxane alkyl structure, it is preferable that there is the organopolysiloxane of epoxycyclohexyethylSiOi alkyl structure。More preferably weight average molecular weight is that the polyorganosiloxane resin containing epoxy radicals of more than 1000 and less than 20,000, preferably more than 1000 and less than 10,000 is it is preferred that have the organopolysiloxane of epoxycyclohexyethylSiOi alkyl structure。

In the present invention, can enumerate especially: by using, there is the compound that the alkoxy silane of expoxycyclohexyl obtains as the sol gel reaction (Sol-GelReaction) of raw material。

Specifically, can enumerate: Japanese Unexamined Patent Publication 2004-256609 publication, Japanese Unexamined Patent Publication 2004-346144 publication, International Publication the 2004/072150th, Japanese Unexamined Patent Publication 2006-8747 publication, International Publication the 2006/003990th, Japanese Unexamined Patent Publication 2006-104248 publication, International Publication the 2007/135909th, Japanese Unexamined Patent Publication 2004-10849 publication, Japanese Unexamined Patent Publication 2004-359933 publication, International Publication the 2005/100445th, what Japanese Unexamined Patent Publication 2008-174640 publication etc. were recorded has the organopolysiloxane of the silsesquioxane type of distribution areolation in three dimensions。

It is not particularly limited for silsesquioxane alkyl structure, but owing to the silicone compounds of simple three-dimensional eyed structure is really up to the mark, it is therefore contemplated that relax the structure of hardness。

In the present invention, it is particularly preferred to 1 molecule is had the block structure body of polysiloxanes segment and the described silsesquioxane alkyl structure obtained by sol gel reaction。Autofrettage as such compound, it is possible to enumerate: International Publication No. 2010/026714 described manufacture method and structure。

In the hardening resin composition of the present invention, the polybasic carboxylic acid (or curing agent composition) of formula (1) can use with the combination of other firming agent。When combination uses, the polybasic carboxylic acid of formula (1) ratio shared by whole firming agent is preferably more than 20 weight %, it is particularly preferred to more than 30 weight %。

As combining, with the polybasic carboxylic acid of formula (1), the firming agent used, it is possible to enumerate such as: aminated compounds, there are the anhydrides compound of unsaturated ring structure, amides compound, phenolic compound, carboxylic acid compound etc.。Concrete example as operable firming agent, it is possible to enumerate: diaminodiphenyl-methane, diethylenetriamines, trien, diamino diphenyl sulfone, isophorone diamine, dicyandiamide, polyamide by linolenic dimer with ethylenediamine synthesis, phthalic anhydride, trimellitic anhydride, PMA, maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylnadic anhydride, carbic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo-[2.2.1] heptane-2,3-dicarboxylic anhydride, methyl bicyclic [2.2.1] heptane-2,3-dicarboxylic anhydride, hexamethylene-1,3,4-tricarboxylic acids-3,4-acid anhydride, bisphenol-A, Bisphenol F, bisphenol S, bis-phenol, terpene diphenol, 4,4'-bis-phenol, 2,2'-bis-phenol, 3,3', 5,5'-tetramethyl-[1,1'-xenyl]-4,4'-glycol, hydroquinone, resorcinol, naphthalene glycol, three (4-hydroxyphenyl) methane, 1,1,2,2-tetra-(4-hydroxyphenyl) ethane, phenols (phenol, the phenol that alkyl replaces, naphthols, the naphthols that alkyl replaces, dihydroxy benzenes, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, benzaldehyde, hydroxy benzaldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, bran aldehyde, 4,4 '-two (chloromethyls)-1,1 '-biphenyl, 4,4 '-two (methoxies)-1,1 '-biphenyl, 1,4 '-two (chloromethyl) benzene, the condensation polymer of 1,4 '-two (methoxy) benzene etc. and their modifier；The halogenated bisphenols classes such as tetrabromobisphenol A；The condensation substance etc. of imidazoles, boron trifluoride-ammonium complex compound, guanidine derivatives, terpene and phenols, but be not restricted to that these。They can be used alone, it is possible to use two or more。

In the hardening resin composition of the present invention, the ratio of firming agent and epoxy resin, epoxy radicals 1 equivalent relative to whole epoxy resin, it is preferable that 0.5 to 1.5 equivalent (thinks the anhydride of the carboxylic acid of 1 official's energy, 1 official's energy), it is particularly preferred to 0.5 to 1.2 equivalent。Relative to epoxy radicals 1 equivalent, if during less than 0.5 equivalent or more than 1.5 equivalent, all likely cannot cure sufficiently and good solidification physical property cannot be obtained。

In the hardening resin composition of the present invention, it is also possible to combine use curing accelerator together with firming agent。Concrete example as operable curing accelerator, it is possible to enumerate: 2-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyano ethyl-2-methylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-cyano ethyl-2-undecyl imidazole, 2,4-diaminourea-6 (2'-Methylimidazole. (1 ')) ethyl s-triazine, 2,4-diaminourea-6 (2 '-undecyl imidazole (1 ')) ethyl s-triazine, 2,4-diaminourea-6 (2 '-ethyl, 4-methylimidazole (1 ')) ethyl s-triazine, 2,4-diaminourea-6 (2 '-Methylimidazole. (1 ')) ethyl s-triazine-isocyanuric acid adduct, the 2:3 addition product of 2-methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-hydroxymethyl-imidazole, 2-phenyl-4-methylol-5-Methylimidazole., 1-cyano ethyl-2-phenyl-3,5-such various the imidazoles of dicyano ethoxyl methyl imidazoles；And, the salt of the polybasic carboxylic acid such as these imidazoles and phthalic acid, M-phthalic acid, p-phthalic acid, trimellitic acid, PMA, naphthalene dicarboxylic acids, maleic acid, oxalic acid；The amide-types such as dicyandiamide；The salt of diaza compound and their tetraphenyl borate, the phenol novolacs etc. such as 1,8-bis-a word used for translation dicyclo [5.4.0] 11-7-alkene；Salt with described polybasic carboxylic acid class or phosphonic acid based；Quaternary ammonium salt (the preferred C of tetrabutylammonium bromide, cetyl trimethylammonium bromide, tricaprylmethyl ammonium bromide, cetyltrimethylammonium hydroxide etc.₁To C₂₀Alkylammonium salt)；Triphenylphosphine, three (toluyl groups) phosphine, tetraphenylphosphonibromide bromideTetraphenylThe phosphonic acid based such as tetraphenyl borate salts orCompound；The phenols such as 2,4,6-triamido sylvan；Amine additives；The metallic compounds etc. such as tin octoate；And the microcapsule-type curing accelerator etc. that will obtain after these curing accelerator micro encapsulation。These curing accelerators are intended to use any, for instance be that the characteristic required by the transparency, curing rate, the such transparent resin composition obtained of operating condition properly selects。The present invention preferably can enumerate:Compound (more preferably seasonSalt) or quaternary ammonium salt。

Curing accelerator, relative to epoxy resin 100 weight portion, generally uses in the scope of 0.001 to 15 weight portion, preferably 0.01 to 5 weight portion, more preferably 0.05 to 1 weight portion。

The hardening resin composition of the present invention can also comprise the phosphorus-containing compound giving composition as anti-flammability。Phosphorus-containing compound can be response type can also be addition type。Concrete example as phosphorus-containing compound, can enumerate: trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricresyl phosphate (xylyl) ester, cresyl phosphate diphenyl ester, cresyl phosphate-2,6-bis-(xyxylene) ester, 1,3-phenylene double; two (two (xyxylene) phosphate ester), 1,4-phenylene double; two (two (xyxylene) phosphate ester), 4, the phosphoric acid ester such as 4 '-biphenyl (two (xyxylene) phosphate ester)；The phosphorus hydrogen types such as 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl)-10H-9-oxa--10-phospho hetero phenanthrene 10-oxide；Phosphorous epoxide that the reactive with active hydrogen of epoxy resin and described phosphorus hydrogen type obtains, red phosphorus etc., preferably phosphoric acid esters, phosphorus hydrogen type or phosphorous epoxide, particularly preferably 1,3-phenylene double; two (two (xyxylene) phosphate ester), 1,4-phenylene double; two (two (xyxylene) phosphate ester), 4,4 '-biphenyl (two (xyxylene) phosphate ester), 4,4 '-butylidene double; two (3-methyl-6-tert butyl phenyl-two-tridecyl phosphite) or phosphorous epoxide。The content of phosphorus-containing compound is preferred with phosphorus-containing compound/whole epoxy resin=0.1 to 0.6 (weight ratio)。When less than 0.1, anti-flammability is insufficient, and time more than 0.6, it is possible to the hygroscopicity of solidfied material, dielectric property are adversely affected。

It addition, in the hardening resin composition of the present invention, it is possible to it is added as needed on antioxidant。As operable antioxidant, it is possible to enumerate: phenol antioxidant, sulphur-containing antioxidant, phosphorous antioxidant etc.。Antioxidant may be used singly or in combination of two or more kinds。Relative to resinous principle 100 weight portion in the hardening resin composition of the present invention, the consumption that makes of antioxidant is generally 0.008 to 1 weight portion, it is preferable that 0.01 to 0.5 weight portion。

As antioxidant, it is possible to enumerate such as: phenol antioxidant, sulphur-containing antioxidant, phosphorous antioxidant etc.。Concrete example as phenol antioxidant, can illustrate: 2,6-ditertbutylparacresol, butylatedhydroxyanisole, 2,6-di-t-butyl is to diethylstilbestrol, β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid stearyl ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) the different monooctyl ester of propanoic acid, 2, double; two (just pungent sulfenyl)-6-(the 4-hydroxyl-3 of 4-, 5-di-tert-butyl aniline)-1,3, the unitary phenols such as 5-triazine, 2,4-double; two [(pungent sulfenyl) methyl] orthoresols；2, 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2, 2 '-di-2-ethylhexylphosphine oxide (4-ethyl-6-tert-butyl phenol), 4, 4 '-thiobis (3-methyl-6-tert butyl phenol), 4, 4 '-butylidene double, two (3-methyl-6-tert butyl phenol), triethylene glycol-bis-[3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], 1, 6-hexanediol-bis-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexa-methylene double, two (3, 5-di-t-butyl-4-hydroxyl-hydrogen-based cinnamamide), 2, 2-sulfenyl-di ethylene bis [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], 3, 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, 3, 9-double, two [1, 1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy } ethyl]-2, 4, 8, 10-tetra-oxaspiro [5.5] hendecane, double, two (3, 5-di-tert-butyl-4-hydroxyl benzyl sulfonic acid) bisphenols such as calcium；1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, four-(methylene-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester) methane, double, two [3, 3 '-bis--(4 '-hydroxyl-3 '-tert-butyl-phenyl) butanoic acid] glyceride, three-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-isocyanuric acid ester, 1, 3, 5-tri-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl)-guanamine, 4, 6-(1H, 3H, 5H) triketone, the polymer electrolyte phenols such as tocopherol。

Concrete example as sulphur-containing antioxidant, it is possible to illustrate: dilauryl-3,3 '-thiodipropionate, myristyl-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate etc.。

Concrete example as phosphorous antioxidant, can illustrate: triphenyl phosphite, diphenyl phosphite isodecyl ester, phenyl-phosphite two isodecyl ester, three (nonyl phenyl) phosphite ester, diiso decyl pentaerythritol phosphite, three (2, 4-di-tert-butyl-phenyl) phosphite ester, double, two (octadecyl) phosphite ester of ring-type neopentane four base, ring-type neopentane four base two (2, 4-di-tert-butyl-phenyl) phosphite ester, ring-type neopentane four base two (2, 4-di-t-butyl-4-aminomethyl phenyl) phosphite ester, the phosphorous acid esters such as double, two [the 2-tert-butyl group-6-methyl-4-{2-(octadecane oxygen base carbonyl) ethyl } phenyl] H-Phosphonate；9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxyl benzyl)-9, the oxa-phospho hetero phenanthrenes such as 10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide, 10-oxygen in last of the ten Heavenly stems base-9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide are oxide-based。

These antioxidants can each be used alone, it is also possible to two or more combination is used。Particularly preferably phosphorous in the present invention antioxidant。

It addition, the hardening resin composition of the present invention can be added as needed on light stabilizer。

As light stabilizer, hindered amine light stabilizer, particularly steric hindrance amine light stabilizer (HALS) are applicable。As HALS, it is not particularly limited, typical example can be enumerated: dibutyl amine-1, 3, 5-triazine-N, N '-bis-(2, 2, 6, 6-tetramethyl-4-piperidyl-1, 6-six methylenediamine and N-(2, 2, 6, 6-tetramethyl-4-piperidyl) condensation polymer of butylamine, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxyl-2, 2, 6, 6-tetramethyl piperidine condensation polymer, poly-[{ 6-(1, 1, 3, 3-tetramethyl butyl) amino-1, 3, 5-triazine-2, 4-bis-base } { (2, 2, 6, 6-tetramethyl-4-piperidyl) imino group } hexa-methylene { (2, 2, 6, 6-tetramethyl-4-piperidyl) imino group }], double, two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) [[3, 5-double, two (1, 1-dimethyl ethyl)-4-hydroxy phenyl] methyl] butylmalonic acid ester, double, two (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate (aftermentioned L1), double, two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, double, two (1-octyloxies-2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, 2-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-2-n-butylmalonic acid double, two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) etc., HALS can only use a kind, can also combine and use two or more。

It addition, in the hardening resin composition of the present invention, resin glue can also be coordinated as required。Resin glue can be enumerated: butyral resinoid, acetal-based resin, acrylic resin, epoxy-nylon-based resin, NBR-phenolic resinoid, epoxy-NBR resinoid, polyamide-based resin, polyimide based resin, polysiloxanes resinoid etc., but be not restricted to that these。The use level of resin glue is added preferably in not damaging in the scope of the anti-flammability of solidfied material, thermostability, relative to resinous principle 100 weight portion, generally can use 0.05 to 50 weight portion, preferably 0.05 to 20 weight portion as required。

In the hardening resin composition of the present invention, it is possible to be added as needed on inorganic filler。Inorganic filler can be enumerated: the powder body such as crystalline silica, melting silicon oxide, aluminium oxide, zircon, calcium silicates, calcium carbonate, carborundum, silicon nitride, boron nitride, zirconium oxide, forsterite, steatite, spinelle, titanium oxide, Talcum or the microballon etc. that will obtain after they ball-types, but is not limited in these。They may be used singly or in combination of two or more。The content of these inorganic fillers can occupy 0 to 95 weight % in the hardening resin composition of the present invention。

It addition, the hardening resin composition of the present invention can add: releasing agents such as silane coupler, stearic acid, Palmic acid, zinc stearate, calcium stearates；Various compounding ingredients, the various heat-curing resins such as zinc compound (metallic soap), surfactant, dyestuff, pigment, UV absorbent such as zinc carbonate (2 ethyl hexanoic acid zinc, zinc stearate, mountain acid zinc, Grillocin P 176) or phosphate ester zinc (octylphosphonic acid zinc, stearyl zinc phosphate etc.)。

As preferred hardening resin composition, it is possible to enumerate following resin combination。

(i) a kind of compositions, it comprises: comprise the epoxy resin of 10 to 90 weight % relative to the total amount of hardening resin composition, relative to epoxy radicals 1 equivalent of this epoxy resin, in the functional equivalent of curing agent composition, comprise the curing agent composition of 0.5 to 1.5 equivalent。This resin combination can also comprise curing accelerator with the ratio of 0.01 to 15 weight portion relative to epoxy resin 100 weight portion。Generally preferable comprise this curing accelerator。

(ii) hardening resin composition as described in above-mentioned (i), wherein, epoxy resin is that (preferable weight-average molecular weight is about 1000 to about 20 for described alicyclic epoxy resin or the organopolysiloxane with epoxycyclohexyethylSiOi alkyl structure, 000, the epoxy radicals organopolysiloxane of more preferably from about 1000 to about 10,000)。

(iii) hardening resin composition as described in above-mentioned (i) or (ii), wherein, alicyclic epoxy resin is the cycloaliphatic epoxy with epoxycyclohexyethylSiOi alkyl structure。

(iv) hardening resin composition as described in above-mentioned (ii) or (iii), wherein, alicyclic epoxy resin is that the expoxycyclohexyl can with methyl is such as with-COO-CH₂-、-COO-(C₃To C₈Divalent representative examples of saturated aliphatic base)-COO-,-CH₂-COO-(C₃To C₈Divalent representative examples of saturated aliphatic base)-COO-or-CH₂-COO-(C₃To C₈Divalent representative examples of saturated aliphatic base)-COO-CH₂-wait the difunctional epoxy resin that linking group is bonded。

V (), if above-mentioned (i) is to the hardening resin composition according to any one of (iv), wherein, firming agent is the polycarboxylic acid compositions described in polybasic carboxylic acid or described 1, described 10 of formula (1)。

(vi) if above-mentioned (i) is to the hardening resin composition according to any one of (iv), wherein, firming agent is the firming agent of the polycarboxylic acid compositions described in polybasic carboxylic acid or described 11 of contained (1)。

(vii) hardening resin composition as according to any one of above-mentioned (i) to (v), wherein, curing agent composition is the polycarboxylic acid compositions described in described 11。

(viii) if above-mentioned (i) is to the hardening resin composition according to any one of (vi), wherein, curing agent composition is the curing agent composition described in described 13。

(ix) if above-mentioned (i) is to the hardening resin composition according to any one of (viii), wherein, the polybasic carboxylic acid of firming agent contained (1) or comprise the firming agent described in described 14。

X (), if above-mentioned (i) is to the hardening resin composition according to any one of (ix), wherein, this curing accelerator isCompound (more preferably seasonSalt) or quaternary ammonium salt。

(xi) if above-mentioned (i) is to the hardening resin composition according to any one of (ix), wherein, the R in formula (1) is methyl or carboxyl。

When the hardening resin composition of the present invention uses in photosemiconductor sealer, it is possible to be added as needed on fluorophor。The effect that fluorophor has is: the blue light that such as sent by blue-led element by absorption portion also sends the sodium yellow that wavelength is converted, is consequently formed white light。In advance fluorophor is dispersed in hardening resin composition, then photosemiconductor is sealed。Fluorophor is not particularly limited, it is possible to use known fluorophor, it is possible to illustrate such as the aluminate of rare earth element, sulfo-gallate, orthosilicate etc.。More specifically, it is possible to enumerate: the fluorophor such as YAG fluorophor, TAG fluorophor, orthosilicate fluorophor, sulfo-gallate fluorophor, sulphide phosphor, it is possible to illustrate: YAlO₃:Ce、Y₃Al₅O₁₂:Ce、Y₄Al₂O₉:Ce、Y₂O₂S:Eu、Sr₅(PO₄)₃Cl:Eu、(SrEu)O·Al₂O₃Deng。The particle diameter of this fluorophor can be used in particle diameter well known in the art, mean diameter preferably 1 to 250 μm, more preferably 2 to 50 μm。When using these fluorophor, its addition is relative to this resinous principle 100 weight portion, it is preferable that 1 to 80 weight portion, more preferably 5 to 60 weight portion。

The hardening resin composition of the present invention can pass through to be obtained by mixing each composition equably。The hardening resin composition of the present invention can by being readily derived its solidfied material with conventional known method same procedure。The method that can enumerate is such as: by the epoxy resin of the present invention and firming agent and curing accelerator as required, phosphorus-containing compound, resin glue, inorganic fill material and compounding ingredient, extruder, kneader, roller etc. is used to be sufficiently mixed to after uniformly as required, obtain hardening resin composition, when this hardening resin composition is liquid, embedding, curtain coating, it is infiltrated up in base material, hardening resin composition is poured in mould, then be heated the method thus solidified；If be solid-state, cast or use transfer formation machine etc. are shaped after melting, then are heated the method thus solidified。Solidification temperature, time are to carry out 2 to 10 hours at 80 to 200 DEG C。As curing, it is possible at high temperature disposal solidifying, but preferably heat up step by step to carry out curing reaction。Specifically, between 80 to 150 DEG C, carry out initial cure, then solidify after carrying out between 100 DEG C to 200 DEG C。Cure stage is preferably divided into 2 to 8 stages and heats up, more preferably 2 to 4 stages。

The hardening resin composition of the present invention is dissolved in toluene, dimethylbenzene, acetone, butanone, methylisobutylketone, dimethylformamide, dimethyl acetylamide, N-methylpyrrole pyridine ketone equal solvent and obtains hardening resin composition varnish, this varnish is infiltrated up in the base materials such as glass fibre, carbon fiber, polyester fiber, Fypro, alumina fibre and paper and heat drying obtains prepreg, by this prepreg by hot-forming, such that it is able to obtain the solidfied material of the hardening resin composition A of the present invention。Solvent now is in the hardening resin composition of the present invention with the mixture of this solvent, it is common to use the amount of 10 to 70 weight %, preferably 15 to 70 weight %。Alternatively, it is also possible to directly fluid composition is obtained the epoxy resin cured product containing carbon fiber by RTM mode。

It addition, the hardening resin composition of the present invention can also use as the modifying agent of film type compositions。Specifically, it is possible to be used for improving the flexibility etc. in B-stage (B-ステジ)。Such pellicular resin compositions can be coated on stripping film by the hardening resin composition A of the present invention is made described hardening resin composition varnish, removes solvent in a heated condition, then carries out B-stage, thus obtain the adhesive of lamellar。This Web-form adhesive can use as the interlayer insulating film in multilager base plate etc.。

Hereinafter, the composition epoxy resin of the present invention encapsulant as photosemiconductor or chip grafting material are described in detail when using。

The composition epoxy resin of the present invention is when the encapsulant of the photosemiconductor as high brightness White LED etc. or chip grafting material use, prepare composition epoxy resin by being sufficiently mixed by the additive of the firming agent (curing agent composition) of the polybasic carboxylic acid of contained (1) Yu epoxy resin and curing accelerator, coupling agent material, antioxidant, light stabilizer etc. to use as encapsulant, or use with encapsulant both sides as chip grafting material。Mixed method uses kneader, three beaming rollers, universal mixer, planet strrier, homogenizer, homogenous disperse machine, ball mill etc. at room temperature or to add warming middle-JIAO and mix。

The photosemiconductors such as high brightness White LED, typically via semiconductor chips such as GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, the InGaN that will be layered on the substrates such as sapphire, spinelle, SiC, Si, ZnO, it is adhesive on lead frame, heat sink or encapsulant forms with adhesive (chip grafting material)。Also there is the type connecting the bonding wires such as gold solder line in order to make current flowing。In order to prevent heat or dampness and in order to realize the effect of lens function, the encapsulants such as this semiconductor chip epoxy resin be sealed。The composition epoxy resin of the present invention can use as this encapsulant or chip grafting material。From the viewpoint of operation, the hardening resin composition of the present invention is all suitable when using as chip grafting material and encapsulant both sides。

The composition epoxy resin of the present invention is by after dispensing (ディスペ Application サ), embedding, silk screen printing coating to use the method that semiconductor chip is adhesive on substrate by the hardening resin composition of the present invention may is that, mounting semiconductor chip is also heating and curing, such that it is able to gluing semiconductor chip。

Heating can use the methods such as heated air circulation type, infrared ray, high frequency。Heating condition preference 80 to about 230 DEG C, about 1 minute to about 24 hours according to appointment。The internal stress produced when being heating and curing to reduce, for instance 80 to 120 DEG C of precuring 30 minutes to 5 hours, can solidify after then carrying out with the condition of 120 to 180 DEG C, 30 minutes to 10 hours。

The molding mode of encapsulant can use as mentioned above: be fixed with injecting sealing material in the frame mould after the substrate of semiconductor chip to loading, is then heated solidifying and the injection mode of molding；Injecting sealing material in a mold in advance, then dipping is fixed on the semiconductor chip on substrate wherein, then from the compression forming mode etc. of mold releasability after heated solidification。

Method for implanting can enumerate such as dispensing, transfer formation, injection moulding etc.。

Heating can use the methods such as heated air circulation type, infrared ray and high frequency。

Heating condition preference 80 to about 230 DEG C, about 1 minute to about 24 hours according to appointment。The internal stress produced when being heating and curing to reduce, for instance 80 to 120 DEG C of precuring 30 minutes to 5 hours, can solidify after then carrying out with the condition of 120 to 180 DEG C, 30 minutes to 10 hours。

Additionally, the hardening resin composition of the present invention is used for the general service of the heat-curing resins such as epoxy resin, specifically, it is possible to enumerate: adhesive, coating, smears, moulding material (including sheet, thin film, FRP etc.), insulant (including printed panel, coating electric wire etc.), encapsulant and encapsulant, substrate cyanate resin composition, as resist firming agent acrylic resin etc., other is to the additive etc. added in resin etc.。

As adhesive, except building is with, for building, automobile, general affairs, therapeutic medical adhesive, it is also possible to enumerate the adhesive of electronic material。Wherein, electronic material sticks with glue agent and can enumerate: the folded interlaminated adhesive increasing the multilager base plates such as (Build-Up) substrate；The adhesive for semiconductor such as chip cement, underfill；BGA enhancing underfill, anisotropic conductive film (ACF), anisotropic conductive paste (ACP) etc. are installed and are sticked with glue agent etc.。

Sealant can be enumerated: capacitor, transistor, diode, light emitting diode, the embedding of IC, LSI etc., dipping, transfer formation sealant；The so-called embedding sealant of COB, COF, TAB etc. of IC, LSI class；The IC such as the underfill of flip-chip etc., QFP, BGA, CSP encapsulates the sealant (comprising enhancing underfill) etc. when class is installed。

The solidfied material of the cured present invention obtained of the hardening resin composition of the present invention may be used for the various uses being representative with optics material。Optics material typicallys represent the material by using in the purposes of this material such as the light that makes visible ray, infrared ray, ultraviolet, X ray, laser。More specifically say, except the LED encapsulant such as lamp-type, SMD type, it is also possible to enumerate example the following stated。The liquid crystal indicator peripheral material of the liquid crystal thin film etc. such as baseplate material in field of liquid crystal, light guide plate, prismatic lens, polaroid, polarizer, angle compensation films, adhesive, polaroid protective film。Additionally, the encapsulant of the color PDP (plasma scope) expected as flat faced display of future generation, antireflective film, optical compensating film, case material, the protective film of front glass, front glass substitution material, adhesive, or the molding material of the LED used in LED display, the encapsulant of LED, the protective film of front glass, front glass substitution material, adhesive, or the baseplate material in plasma addressed liquid (PALC) display, light guide plate, prismatic lens, polaroid, polarizer, angle compensation films, adhesive, polarizer protective films, or the protective film of the front glass in organic EL (electroluminescent) display, front glass substitution material, adhesive, or the various film substrates in Field Emission Display (FED), the protective film of front glass, front glass substitution material, adhesive。In optical recording field, there are VD (optic disc), CD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (phase transition optical disk), the CD substrate material of light-card, pickup lens, protective film, encapsulant, adhesive etc.。

In field of optical equipment, there are the camera lens material of still camera, range finder prism, target prism, view finder cover, optical receiving sensor portion。It addition, have the taking lens of video camera, view finder。It addition, have the projection lens of projecting television set, protective film, encapsulant, adhesive etc.。The camera lens material of lighting apparatus, encapsulant, adhesive, thin film etc.。In optics field, there are the fibrous material of optical switch periphery in optical communication system, lens, waveguide, the encapsulant of element, adhesive etc.。The fiber optic materials of optical conenctor periphery, lasso, encapsulant, adhesive etc.。In passive optical parts, optical circuit parts, there are lens, waveguide, the encapsulant of LED, the encapsulant of CCD, adhesive etc.。The baseplate material of optoelectronic integrated circuit (OEIC) periphery, fibrous material, the encapsulant of element, adhesive etc.。In field fiber, have decorative display illumination/photoconduction etc., the sensor class of industrial use, display/mark class etc. and the communications infrastructure with and family in the optical fiber that connects of digital equipment。In semiconductor integrated circuit peripheral material, there is the anticorrosive additive material of the microlithography of LSI, super LSI material。In automobile, transporter field, there are the lamp reflector of automobile, retainer, gear parts, anti-corrosion coating, switch sections, headlight, engine interior part, electric component, various inside and outsides parts, drive electromotor, braking fuel tank, automobile Rustproof Steel Plate, trim panel, interior material, protection/tie up with wire harness, fuel hose, auto lamp, glass substitute。It addition, there is the compound glass of rolling stock。It addition, have the toughener of the structural material of aircraft, electromotor peripheral member, protection/tie up with wire harness, anti-corrosion coating。In building field, there are interior packing/factorial lumber material, electrical equipment cover (カバ), sheet material (シト), middle membrane of glass, glass substitute, solaode peripheral material。In agricultural use, there is plastic house thin film。As follow-on optoelectronic function organic material, have organic EL element peripheral material, organic photorefractive element, as the peripheral baseplate material of the light amplifying component of light-light conversion device, optical operation element, organic solar batteries, fibrous material, the encapsulant of element, adhesive etc.。

Sealant can be enumerated such as: capacitor, transistor, diode, light emitting diode, the embedding of IC, LSI etc., dipping, transfer molding sealant；The embedding sealant of COB, COF, TAB etc. of IC, LSI class；The IC such as the underfill of flip-chip etc., BGA, CSP encapsulates the sealant (comprising enhancing underfill) etc. when class is installed。

Other purposes of optics material, the general service using hardening resin composition A or hardening resin composition B can be enumerated, it is possible to enumerate such as: adhesive, coating, smears, moulding material (including sheet, thin film, FRP etc.), insulant (including printed base plate, coating electric wire etc.), sealant and other additive etc. added in resin etc.。As adhesive, it is possible to enumerate the adhesive of building use, for building, automobile use, general affairs use, therapeutic medical adhesive and electronic material。Wherein, electronic material sticks with glue agent and can enumerate: the folded interlaminated adhesive increasing the multilager base plates such as substrate；The adhesive for semiconductor such as chip cement, underfill；BGA enhancing underfill, anisotropic conductive film (ACF), anisotropic conductive paste (ACP) etc. are installed and are sticked with glue agent etc.。

Embodiment

Hereinafter, further illustrating the present invention by embodiment, in following description, if not otherwise specified, " part " refers to weight portion。It addition, the invention is not restricted to these embodiments。It addition, in the present invention, the condition determination of gel permeation chromatography (hereinafter referred to as GPC) is as described below。Pillar uses Shode × SYSTEM-21 post (KF-803L, KF-802.5 (× 2), KF-802), eluent is oxolane, flow velocity is 1ml/ minute, column temperature is 40 DEG C, additionally, detection uses RI (reflectance) to carry out, and standard curve uses the Shodex polystyrene standard manufactured。It addition, functional equivalent is calculated by the ratio tried to achieve by GPC, and obtain respectively by carboxylic acid, anhydride is set to 1 equivalent time value。

Embodiment 1 (polycarboxylic acid compositions A1)

In the flask possessing agitator, reflux condensing tube and agitating device, carry out nitrogen purging be simultaneously introduced toluene 10 parts, 2,4-diethyl-1,5-PD (Kyowa Yuka Kk manufacture；キョウワジオ Le PD9) 80 parts, (new Japan Chemical (Co., Ltd.) manufactures for the mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride；RikacidMH700 ratio 7:3, hereinafter referred to as anhydride H1) 168 parts, carry out 4 hours heated and stirred at 100 DEG C。At this moment, confirm that the disappearance (1 below area %) of raw material terminates reaction afterwards by GPC。After terminating reaction, use Rotary Evaporators, the solvent of residual is carried out distillation and removes and obtain the polycarboxylic acid compositions (A1) 246 parts of the present invention。Gains are colorless solid resin, are 97 area % by the GPC polybasic carboxylic acid content measured。It addition, functional equivalent's (being hereinafter referred merely to as functional equivalent) that carboxyl and anhydride are added together is 245g/eq.。Though it addition, shape is solid-state, but somewhat there is mobility, at room temperature slowly deforming and having close to semi-solid shape。

Embodiment 2 (curing agent composition B1)

Relative to the polycarboxylic acid compositions (A1) 25 parts obtained in embodiment 1, add 75 parts of anhydride (H1) and make its uniform dissolution, obtain the curing agent composition (B1) of the present invention。Viscosity at 50 DEG C is 450mPa s (E type viscometer)。

Embodiment 3 (curing agent composition B2)

In the flask possessing agitator, reflux condensing tube and agitating device, at 2, the 4-diethyl-1,5-PD that is simultaneously introduced carrying out nitrogen purging, (Kyowa Yuka Kk manufactures；キョウワジオ Le PD9) 20 parts, 100 parts of anhydride (H1), carry out 4 hours heated and stirred at 60 DEG C。Confirm that 2,4-diethyl-1,5-pentanediol is 1 below area % by GPC。Obtain the curing agent composition (B2) 120 parts comprising polycarboxylic acid compositions of the present invention。The reaction product obtained is colorless liquid resin。By the GPC proportion of composing measured it is: polybasic carboxylic acid (A1) is the total amount of 52 area %, methylhexahydrophthalic anhydride and hexahydrophthalic anhydride is 48 area %。It addition, functional equivalent is 197g/eq.。Viscosity at 50 DEG C is that 1340mPa s is (for 19700mPa s at 25 DEG C；E type viscometer)。

Embodiment 4,5 (hardening resin composition)

Firming agent uses curing agent composition B1 and B2 of the present invention obtained by embodiment 2 and 3, epoxy resin to use 3,4-epoxycyclohexylmethyl-3,4-expoxycyclohexyl carboxylate respectively, and (DowChemical manufactures；UVR-6105, hereinafter referred to as epoxy resin (EP-1)), curing accelerator use cetyltrimethylammonium hydroxide (Tokyo HuaCheng Industry Co., Ltd manufacture；25% methanol solution, hereinafter referred to as C1), coordinate with the mixing ratio (weight portion) shown in table 1 below, after carrying out the deaeration of 20 minutes, obtain the hardening resin composition of the present invention。

Comparative example 1 (comparing with hardening resin composition)

In above-described embodiment 4 and 5, except firming agent is changed to anhydride (H1), carries out same operation with embodiment 4 and 5, obtain the hardening resin composition compared。

Use the hardening resin composition obtained, carry out volatilization test and LED test with the main points shown in following, and their result is shown in table 1。It addition, condition of cure is after the precuring of 120 DEG C × 2 hours 150 DEG C × 5 hours。

Volatilization test:

After hardening resin composition that embodiment 4,5 and comparative example 1 are obtained implements vacuum defoamation 20 minutes, it is poured into lentamente in the cofferdam made on the glass substrate with heat resistant adhesive tape and obtains 30mm × 20mm × height 1mm。After measuring the weight resin of cast exactly, this casting is made to solidify with described condition。

Measure the weight of the solidfied material so obtained, confirm that weight when solidifying reduces。It addition, any one in embodiment 4,5 and comparative example 1 all similarly solidifies under same baking oven。

LED tests:

After each hardening resin composition that embodiment 4,5 and comparative example 1 obtain is carried out vacuum defoamation 20 minutes, it is filled in respectively in barrel。Accurate discharger is used to be poured into respectively in surface installing type (the SMD type 3mm φ) LED of the light-emitting component being respectively equipped with emission wavelength 465nm。Then, make them solidify under above-mentioned condition of cure, obtain test LED。

Assessment item and metewand:

(a) volatility: whether the solidfied material surface after sealing with visualization has pit and be evaluated。Metewand in table is as described below。

Zero: do not observe pit；

△: observe a small amount of pit；

×: observe a large amount of pit (occurring that bonding wire exposes)。

B () Reflow Soldering is tested: after the test LED obtained was carried out moisture absorption at 30 DEG C, 70% × 72 hour under condition, uses high temperature observation device (SMTScopeSK-5000；Adret Jinggong Co., Ltd manufactures), confirm that LED has crack-free to produce when following Reflow Soldering。Test carries out when n=3, is evaluated with (OK number)/(test number)。It addition, above-mentioned (OK number) refers to does not observe the passing number produced that breaks。

Condition is: be warming up to 150 DEG C by 25 DEG C with 2 DEG C/sec, then at 150 DEG C keep 2 minutes, then 2 DEG C/sec be warming up to 260 DEG C and keep 10 seconds after, be cooled to room temperature with 1.3 DEG C/sec。

Table 1

Embodiment 4,5 and comparative example 1 being compared, the volatile quantity of the hardening resin composition of the present invention is few, even if when sealing LED without producing the problems such as bonding wire exposes。It addition, also can't see the generation broken when Reflow Soldering。From the above results, used as firming agent by the curing agent composition of the polycarboxylic acid compositions that will comprise the present invention and the present invention of anhydride, it is possible to obtain the hardening resin composition that volatility resistance and the reflux-resisting welded excellent solidfied material that breaks can be provided。

Embodiment 6 (curing agent composition B3)

In the flask possessing agitator, reflux condensing tube and agitating device, at 2, the 4-diethyl-1,5-PD that is simultaneously introduced carrying out nitrogen purging, (Kyowa Yuka Kk manufactures；キョウワジオ Le PD9) 12 parts, 73 parts of anhydride (H1), (H-TMAn Rhizoma Sparganii gas chemistry manufactures 1,2,4-cyclohexanetricarboxylic acid's-1,2-acid anhydride；Hereinafter referred to as H2) 15 parts, carry out 4 hours heated and stirred at 60 DEG C。Confirm that 2,4-diethyl-1,5-pentanediol is terminate reaction after 1 below area % by GPC。

Obtain the curing agent composition (B3) 100 parts of the polybasic carboxylic acid of contained (1) and the present invention of anhydride。Gains are colourless liquid resin。Functional equivalent is 183g/eq.。Viscosity at 50 DEG C is 1010mPa s。

Embodiment 7 (curing agent composition B4)

In the flask possessing agitator, reflux condensing tube and agitating device, at 2, the 4-diethyl-1,5-PD that is simultaneously introduced carrying out nitrogen purging, (Kyowa Yuka Kk manufactures；キョウワジオ Le PD9) 20 parts, (the new Japan Chemical manufacture of 4-hexahydrotoluene dicarboxylic anhydride；RikacidMHH3) 100 parts, 4 hours heated and stirred are carried out at 60 DEG C。Confirm that 2,4-diethyl-1,5-pentanediol is 1 below area % by GPC。Obtain the polybasic carboxylic acid of contained (1) and the curing agent composition (B4) 120 parts of anhydride。Functional equivalent is 201g/eq.。Viscosity at 50 DEG C is that 1100mPa s is (for 16200mPa s at 25 DEG C；E type viscometer)。

Embodiment 7a

Use Rotary Evaporators, at 100 to 150 DEG C, the methylhexahydrophthalic anhydride being present in excess is removed (from the moment that methylhexahydrophthalic anhydride no longer flows out from curing agent composition (B4) 50 parts, it is passed directly into nitrogen 40 minutes under heating reduced pressure, anhydride can be removed fully), thus take out the polycarboxylic acid compositions (B4a) 25 parts of the present invention。It is shaped as colourless semi-solid-state to solid-state resin。

The softening point (according to JISK-7234) of gained resin is 58.9 DEG C, and the melt viscosity at 150 DEG C is 0.08Pa s。

Embodiment 8 (curing agent composition B5)

In the flask possessing agitator, reflux condensing tube and agitating device, at 2, the 4-diethyl-1,5-PD that is simultaneously introduced carrying out nitrogen purging, (Kyowa Yuka Kk manufactures；キョウワジオ Le PD9) 12 parts, 73 parts of anhydride (H3), 15 parts of anhydride (H2), carry out 4 hours heated and stirred at 60 DEG C。Confirm that 2,4-diethyl-1,5-pentanediol is 1 below area % by GPC。Obtain the polybasic carboxylic acid of contained (1) and the curing agent composition (B5) 100 parts of anhydride。Gains are colourless liquid resin。Functional equivalent is 186g/eq.。Viscosity at 50 DEG C is 1050mPa s。

Embodiment 9 (curing agent composition B6)

In the flask possessing agitator, reflux condensing tube and agitating device, at 2, the 4-diethyl-1,5-PD that is simultaneously introduced carrying out nitrogen purging, (Kyowa Yuka Kk manufactures；キョウワジオ Le PD9) 20 parts, cyclohexane dicarboxylic acid acid anhydride 100 parts, carry out 4 hours heated and stirred at 60 DEG C。Confirm that 2,4-diethyl-1,5-pentanediol is 1 below area % by GPC。Obtain the polybasic carboxylic acid of contained (1) and the curing agent composition (B6) 120 parts of anhydride。Functional equivalent is 188g/eq.。Viscosity at 50 DEG C is 1200mPa s (E type viscometer)。

Synthesis example 1 (compare and use curing agent composition B7)

In the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced 1,4-CHDM (new Japan Chemical manufacture what carry out nitrogen purging；SKY-CDM) 20 parts, 100 parts of anhydride (H1), carry out 4 hours heated and stirred at 60 DEG C。Obtain the curing agent composition (B7) 120 parts comprising polybasic carboxylic acid and anhydride of comparative example。It addition, functional equivalent is 171g/eq.。Viscosity at 25 DEG C is 18900mPa s (E type viscometer)。

Synthesis example 2 (compare and use curing agent composition B8)

In the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced neopentyl glycol 20 parts, 100 parts of anhydride (H1) what carry out nitrogen purging, carries out 4 hours heated and stirred at 60 DEG C。Obtain the curing agent composition (B8) 120 parts comprising polybasic carboxylic acid and anhydride of comparative example。Functional equivalent is 197g/eq.。Viscosity at 25 DEG C is 23800mPa s (E type viscometer)。

Synthesis example 3 (compare and use curing agent composition B9)

In the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced 1,6-hexanediol 20 parts, 100 parts of anhydride (H1) what carry out nitrogen purging, carries out 4 hours heated and stirred at 60 DEG C。Obtain the curing agent composition (B9) 120 parts comprising polybasic carboxylic acid and anhydride of comparative example。It addition, functional equivalent is 197g/eq.。Viscosity at 25 DEG C is 15600mPa s (E type viscometer)。

Synthesis example 4 (epoxy resin-2)

Reaction vessel adds β-(3,4-expoxycyclohexyl) ethyl trimethoxy silane 106 parts, the silanol stopped methyl phenyl silicone oil 234 parts (silanol equivalent weight 850, according to using GPC measures the 1/2 of weight average molecular weight to be calculated) of weight average molecular weight 1700 (GPC measured value) and 0.5% potassium hydroxide (KOH) methanol solution 18 parts, bath temperature is set in 75 DEG C and heats up。After intensification, reaction 8 hours under reflux。

Then, add after methanol 305 parts, with the methanol solution (concentration is 50 weight %) 86.4 parts of 60 minutes dropping distilled water, react 8 hours at 75 DEG C under reflux。Reaction terminate after, with in the biphosphate sodium water solution of 5% and after, at the methanol of 80 DEG C of Distillation recoveries about 90%。Add methylisobutylketone 380 parts, and repeat 3 washings with the water of 200 parts。Then, by using Rotary Evaporators by organic phase solvent under reduced pressure, remove at 100 DEG C, the epoxy resin (EP-2) 300 parts with siloxane structure is thus obtained。The epoxide equivalent of gained compound is 729g/eq, weight average molecular weight is 2200, and outward appearance is water white transparency。

Synthesis example 5 (the starting compound D-1 of epoxy resin)

In the flask possessing agitator, reflux condensing tube, agitating device and Dean-Stark (Dean-stark) pipe, carry out nitrogen purging be simultaneously introduced Isosorbide-5-Nitrae-cyclohexanedicarboxylate (rock GUWA this manufacture；DMCD-p) 140 parts, cyclohexene-4-methanol 314 parts, four titanium butoxide 0.07 part, within 12 hours, react with 120 DEG C 1 hour, 150 DEG C 1 hour, 170 DEG C 1 hour, 190 DEG C, simultaneously remove reaction in generate methanol。After confirming that raw material crest is 1 below area % by gas chromatogram (GC), it is cooled to 50 DEG C。

After cooling terminates, add the toluene of 347 parts and make it uniform, then, reaction solution being carried out 3 washings with the sodium hydrate aqueous solution 80 parts of 10 weight %, being then repeatedly performed washing till waste water becomes neutrality with the water of 100 parts/time。Using Rotary Evaporators under heating decompression, toluene and unreacted 3-cyclohexene-1-methanol are removed in distillation。Obtain compound (D-1) 240 parts that be main constituent with double; two (3-cyclohexenyl methyl)-1,4-cyclohexane dicarboxylic acid, that under room temperature be liquid。

Synthesis example 6 (epoxy resin-3)

In the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced, what carry out nitrogen purging, the compound (D-1) 118 parts that 15 parts of water, 12-tungstophosphoric acid 0.95 part, disodium hydrogen phosphate 0.78 part, 50% xylene solution 2.7 parts of trioctylphosphine ammonium acetate, toluene 180 parts and synthesis example 5 obtain。By this solution warms to 60 DEG C, while carrying out the stirring of fierceness, adding 35 weight % aqueous hydrogen peroxide solution 70 parts with 1 hour, former state stirs 13 hours at 60 DEG C。By gas chromatogram confirm reaction carry out to raw material crest be 1 below area %。

Then, with in 1 weight % sodium hydrate aqueous solution and after, add 20 weight % sodium thiosulfate solution 25 parts and stir and stand after 30 minutes。Taking out organic layer after being separated into 2 layers, (aginomoto fine chemistry manufactures to add activated carbon wherein；CP1) 20 parts, bentonite (ホジュ Application manufactures ベ Application ゲ Le SH) 20 parts, at room temperature stirring was filtered after 1 hour。With 100 parts of water, gained filtrate is carried out 3 times to wash, and remove toluene from the organic layer distillation obtained, thus obtain the epoxy resin (EP-3) 119 parts for liquid under room temperature。The epoxide equivalent of gained epoxy resin is 217g/eq.。Viscosity at 25 DEG C is 9200mPa s (E type viscometer)。

Synthesis example 7 (the raw material diolefin compound D-2 of epoxy resin)

With reference to PCT/JP2009/067432, in the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced 150 parts of water, 55.1 parts of 3-cyclohexene formaldehyde, 62.6 parts of double; two (trihydroxy methyl) propane, concentrated hydrochloric acid 7.3 parts what carry out nitrogen purging, at 60 DEG C, reacts 10 hours。After reaction terminates, reactant liquor adds 10 parts of water, 3% sodium hydrate aqueous solution 30 parts, then, this reactant liquor dibastic sodium phosphate is neutralized。Being added thereto to methylisobutylketone 200 parts, after carrying out 3 washings with 100 parts of water, solvent etc. is removed in distillation, thus obtains diolefin compound (D-2) 101 parts。

Synthesis example 8 (epoxy resin-4)

With reference to PCT/JP2009/067432, in the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced in 15 parts of water, 12-tungstophosphoric acid 0.47 part, disodium hydrogen phosphate 0.39 part, 50% xylene solution 1.4 parts of trioctylphosphine ammonium acetate, toluene 90 parts and synthesis example 7, what carry out nitrogen purging, the compound (D-2) 54 parts obtained。By this solution warms to 60 DEG C, adding 35 weight % aqueous hydrogen peroxide solution 35 parts with 1 hour while carrying out the stirring of fierceness, former state stirs 13 hours at 60 DEG C。By gas chromatogram confirm reaction carry out to raw material crest be 1 below area %。

Then, with in 1 weight % sodium hydrate aqueous solution and after, add 20 weight % sodium thiosulfate solution 12 parts, after stir 30 minutes standing。Taking out and be separated into the organic layer after 2 layers, (aginomoto fine chemistry manufactures to add activated carbon wherein；CP1) 10 parts, montmorillonite (Network ニミネ work manufacture；Network ニピア F) 10 parts, at room temperature stirring was filtered after 3 hours。With 100 parts of water, gained filtrate is carried out 3 times to wash, and remove toluene from the organic layer distillation obtained。Obtain the epoxy resin (EP-4) 49 parts for liquid under room temperature。The epoxide equivalent of gained epoxy resin is 262g/eq.。Viscosity at 25 DEG C is 230000mPa s (E type viscometer)。

Embodiment 10 (hardening resin composition)

Epoxy resin use synthesis example 4 obtain epoxy resin (EP2), firming agent use embodiment 3 obtain curing agent composition (B2), curing accelerator use seasonSalt (Japan Chemical Industry manufacture；ヒシ U リ Application PX4MP, hereinafter referred to as C2), additive uses double; two (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Japan's vapour bar manufactures；TINUVIN770DF, hereinafter referred to as L1) and phosphorus-containing compound use 4, (ADEKA manufactures 4 '-butylidene double; two (3-methyl-6-tert butyl phenyl-two-tridecyl phosphate esters)；アデカスタ Block 260, hereinafter referred to as M1), coordinate with the mixing ratio (weight portion) shown in table 2 below, after carrying out the deaeration of 20 minutes, obtain the hardening resin composition of the present invention。It is occur so that with time limit (pot-life) test with aftermentioned method for gained hardening resin composition。By result and remember in table 2 below。

By gained hardening resin composition injection testing sheet die for molding lentamente, obtain the solidfied material of various test so that the condition of 150 DEG C × 1 hour after the precuring of 120 DEG C × 3 hours makes this casting solidify。For gained solidfied material, carry out following heat durability absorbance test according to the condition of following record, LED bright light is tested and is evaluated。Result is illustrated in together table 2 below。

Can useful life

Viscosity B coefficent when at room temperature placing after making for hardening resin composition, is measured with after 6 hours after 3 hours。Then, it is evaluated with its viscosity climbing (in time through viscosity later/initial stage viscosity × 100) (%)。

Heat durability absorbance is tested

Heat resistant test condition: place 96 hours in 150 DEG C of baking ovens

Test film size: thickness 1mm

Appreciation condition: use the absorbance of spectrophotometric determination 400nm。And calculate its rate of change。

LED bright light is tested

Gained hardening resin composition is filled in barrel and uses accurate discharger to be poured in surface mounting LED encapsulation (internal diameter 4.4mm, outer wall height 1.25mm) square for external diameter 5mm of the chip being equipped with center luminescence ripple 465nm。This casting is put into heating furnace, carries out 120 DEG C, 1 hour, the cured of then 150 DEG C, 3 hours, obtain LED encapsulation。After being installed by LED, measuring illumination after making LED bright light with following condition, result is shown in table 2。

Bright light detailed conditions

Emission wavelength: 465nm

Type of drive: constant current behavior, 60mA (light-emitting component scheduled current is 30mA)

Drive environment: 85 DEG C, 85%

Driving time: 200 hours, 400 hours

Evaluate: the illumination conservation rate after bright light

Comparative example 2,3,4

In above-described embodiment 10, except firming agent is changed to curing agent composition B7, B8 or B9 that synthesis example 1,2 or 3 obtains, operate similarly to Example 10, obtain the hardening resin composition compared。For each hardening resin composition obtained, occur so that similarly to Example 10 and test with the time limit。Result is recorded in table 2 below。

It addition, the hardening resin composition that above-mentioned gained is compared, solidify similarly to Example 10, for gained solidfied material, carry out following heat durability absorbance test according to the condition of following record, LED bright light is tested and is evaluated。Result is illustrated in together table 2 below。

Table 2

By result above it can be seen that the viscosity climbing of the hardening resin composition of the present invention is low, have longer can useful life。In addition we know, using the polycarboxylic acid compositions of the present invention and the solidfied material that obtains, compared with the solidfied material obtained with using other skeleton, the illumination conservation rate in LED situation is excellent and excellent optical characteristics。

Embodiment 11,12 (hardening resin composition)

Epoxy resin uses the epoxy resin (EP-3, EP-4) obtained in synthesis example 6,8, firming agent to use the curing agent composition (B4) obtained in embodiment 7, curing accelerator to use seasonSalt (Japan Chemical Industry manufacture；ヒシ U リ Application^RTMPX4MP, hereinafter referred to as C2), additive uses double; two (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Japan's vapour bar manufactures；TINUVIN770DF, hereinafter referred to as L1) and phosphorus-containing compound use 4, (ADEKA manufactures 4 '-butylidene double; two (3-methyl-6-tert butyl phenyl-two-tridecyl phosphate esters)；アデカスタ Block 260, hereinafter referred to as M1), coordinate with the mixing ratio (weight portion) shown in Table 3 below, after carrying out the deaeration of 20 minutes, obtain the hardening resin composition of the present invention。

Gained hardening resin composition is poured in test film mould lentamente, obtains the solidfied material of various test so that the condition of 150 DEG C × 1 hour after the precuring of 120 DEG C × 3 hours makes this casting solidify。For gained solidfied material, carry out following LED bright light according to the condition of following record and test and be evaluated。Result is illustrated in together Table 3 below。

LED bright light is tested

Gained hardening resin composition is filled in barrel and uses accurate discharger to be poured in surface mounting LED encapsulation (internal diameter 4.4mm, outer wall height 1.25mm) square for external diameter 5mm of the chip being equipped with center luminescence ripple 465nm。This casting is put into heating furnace, carries out 120 DEG C, 1 hour, the cured of then 150 DEG C, 3 hours, obtain LED encapsulation。After LED is encapsulated, measure illumination after making LED bright light with following condition, show the result in table 3。

Bright light detailed conditions

Emission wavelength: 465nm

Drive environment: 85 DEG C, 85%

Driving time: 200 hours

Evaluate: bright light illumination conservation rate after 200 hours

Table 3

Embodiment 13,14,15 (hardening resin composition)

Epoxy resin uses epoxy resin (EP-1, EP-3), firming agent use the curing agent composition (B2, B4, B6) obtained in embodiment and use curing accelerator (C2), coordinate with the mixing ratio (weight portion) shown in table 4 below, after carrying out the deaeration of 20 minutes, obtain the hardening resin composition of the present invention。

Gained hardening resin composition is poured in test film mould lentamente, obtains the solidfied material of various test so that the condition of 150 DEG C × 1 hour after the precuring of 110 DEG C × 3 hours makes this casting solidify。For gained solidfied material, carry out following LED bright light according to the condition of following record and test and be evaluated。Result is illustrated in together table 4 below。

LED bright light is tested

Gained hardening resin composition is filled in barrel and uses accurate discharger to be poured in surface mounting LED encapsulation (internal diameter 4.4mm, outer wall height 1.25mm) square for external diameter 5mm of the chip being equipped with center luminescence ripple 465nm。This casting is put into heating furnace, carries out 120 DEG C, 1 hour, the cured of then 150 DEG C, 3 hours, obtain LED encapsulation。After LED is encapsulated, measure illumination after making LED bright light with following condition, show the result in table 4。

Bright light detailed conditions

Emission wavelength: 465nm

Drive environment: 85 DEG C, 85%

Driving time: 200 hours

Evaluate: bright light illumination conservation rate after 200 hours

Table 4

Embodiment 16,17,18 (hardening resin composition)

Epoxy resin uses epoxy resin (EP-1, EP-3), firming agent use the curing agent composition (B3, B5) obtained in anhydride (H1, H2) embodiment and use curing accelerator (C2), coordinate with the mixing ratio (weight portion) shown in table 5 below, after carrying out the deaeration of 20 minutes, obtain the hardening resin composition of the present invention。

Gained hardening resin composition is poured in test film mould lentamente, obtains the solidfied material of various test so that the condition of 150 DEG C × 1 hour after the precuring of 110 DEG C × 3 hours makes this casting solidify。For gained solidfied material, carry out following LED bright light according to the condition of following record and test and be evaluated。Result is illustrated in together table 5 below。

LED bright light is tested

Bright light detailed conditions

Emission wavelength: 465nm

Drive environment: 85 DEG C, 85%

Driving time: 200 hours

Evaluate: bright light illumination conservation rate after 200 hours

Comparative example 5,6 (hardening resin composition compared)

In above-described embodiment 15,16 and 17, except firming agent is changed to anhydride H1 or H2, operate equally, obtain the hardening resin composition compared。It addition, with above-described embodiment 15,16 and 17 same operate, solidify, for each solidfied material obtained, also carry out LED bright light test in the same manner as this embodiment。Result is illustrated in together table 5 below。

Table 5

Embodiment b1 (polycarboxylic acid compositions Ab1)

In the flask possessing agitator, reflux condensing tube and agitating device, carry out nitrogen purging be simultaneously introduced toluene 10 parts, Tricyclodecane Dimethanol (OXEA manufacture；TCD-AlcholDM) (new Japan Chemical (Co., Ltd.) manufactures the mixture (7:3) of 98 parts, methylhexahydrophthalic anhydride and hexahydrophthalic anhydride；RikacidMH700, hereinafter referred to as anhydride H1) 168 parts, carry out 15 minutes, 100 DEG C at 80 DEG C and carry out the heated and stirred of 4 hours。Confirm that raw material is 1 below area % by GPC。After terminating reaction, use Rotary Evaporators, the distillation of the solvent of residual is removed。Obtain the polycarboxylic acid compositions (Ab1 of the present invention；The mixture of the structural formula of following formula (3)) 246 parts。Gains are colorless solid resin, and softening point is 74 DEG C。It addition, melt viscosity is 0.22Pa S at 150 DEG C。It is 99 area % by the GPC purity measured。It addition, functional equivalent is 266g/eq.。

Formula (3):

R=CH₃Or H

Embodiment b2 (curing agent composition Bb1)

Relative to the polycarboxylic acid compositions (Ab1: the mixture of the structural formula of formula (3)) 25 parts obtained in embodiment b1, add 75 parts of anhydride (H1) and make its uniform dissolution, thus obtaining the curing agent composition (Bb1) of the present invention。

Embodiment b3 (curing agent composition Bb2)

In the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced Tricyclodecane Dimethanol 20 parts, 100 parts of anhydride (H1) what carry out nitrogen purging, carries out the heated and stirred of 4 hours at 50 DEG C。Confirm that Tricyclodecane Dimethanol is 1 below area % by GPC。Obtain the curing agent composition (Bb2) 120 parts comprising polycarboxylic acid compositions of the present invention。Gains are colourless liquid resin, by the GPC purity measured, and polycarboxylic acid compositions (Ab2；The mixture of the structural formula of formula (3)) the total amount that structure is 43 area %, methylhexahydrophthalic anhydride and hexahydrophthalic anhydride be 57 area %。It addition, functional equivalent is 199g/eq.。

Embodiment b4, b5 (hardening resin composition), comparative example b1 (comparing with hardening resin composition)

Firming agent uses the curing agent composition (Bb1) of the present invention, (Bb2) that embodiment b2, b3 obtain, and the anhydride of comparative example (H1)；Epoxy resin uses 3,4-epoxycyclohexylmethyl-3,4-expoxycyclohexyl carboxylate, and (DowChemical manufactures；UVR-6105, hereinafter referred to as epoxy resin (EP-1))；Curing accelerator uses cetyltrimethylammonium hydroxide, and (Tokyo HuaCheng Industry Co., Ltd manufactures；25% methanol solution, hereinafter referred to as C1), coordinate with the mixing ratio (weight portion) shown in following table b1, after carrying out the deaeration of 20 minutes, obtain the present invention or the hardening resin composition compared。

Use the hardening resin composition obtained, carry out volatilization test, LED leakage test with the main points shown in following, and show the result in table b1。It addition, condition of cure is after the precuring of 120 DEG C × 2 hours 150 DEG C × 5 hours。

Volatilization test:

The hardening resin composition obtained in embodiment and comparative example, after implementing vacuum defoamation 20 minutes, is poured into lentamente in the cofferdam made on the glass substrate with heat resistant adhesive tape and obtains 30mm × 20mm × height 1mm。After measuring the weight resin of cast exactly, this casting is made to solidify with described condition。

Measure the weight of the solidfied material so obtained, confirm that weight when solidifying reduces。(embodiment, comparative example be solidificated under same baking oven and similarly solidify)。

LED tests:

After hardening resin composition embodiment and comparative example obtained carries out vacuum defoamation 20 minutes, it is filled in barrel, uses accurate discharger to be poured in surface installing type (the SMD type 3mm φ) LED of the light-emitting component being equipped with emission wavelength 465nm。Then, make them solidify under predetermined condition of cure, obtain test LED。

Assessment item:

(a) volatility: whether the solidfied material surface after sealing with visualization has pit and be evaluated。In table, zero: do not observe pit；△: observe a small amount of pit；×: observe a large amount of pit (occurring that bonding wire exposes)。

B () Reflow Soldering is tested: after the test LED obtained was carried out moisture absorption at 30 DEG C, 70% × 72 hour under condition, uses high temperature observation device (SMTScopeSK-5000；Adret Jinggong Co., Ltd manufactures), confirm that LED has crack-free to produce when following Reflow Soldering。Test carries out when n=3, is evaluated with (OK number)/(test number)。Condition is: be warming up to 150 DEG C by 25 DEG C with 2 DEG C/sec, then at 150 DEG C keep 2 minutes, then 2 DEG C/sec be warming up to 260 DEG C and keep 10 seconds after, be cooled to room temperature with 1.3 DEG C/sec。

Table b1

Embodiment b4, b5 and comparative example b1 being compared, the volatile quantity of the hardening resin composition of the present invention is few, though the problem such as also do not produced that bonding wire exposes when sealing LED。It addition, breaking during Reflow Soldering can also be reduced。From the above results, the polycarboxylic acid compositions of the present invention and the curing agent composition that comprises polycarboxylic acid compositions may provide for volatility resistance, the reflux-resisting welded effective hardening resin composition that breaks。

Embodiment b6 (curing agent composition Bb3)

In the flask possessing agitator, reflux condensing tube and agitating device, carry out nitrogen purging be simultaneously introduced Tricyclodecane Dimethanol 20 parts, methylhexahydrophthalic anhydride (new Japan Chemical (Co., Ltd.) manufacture；RikacidMH, hereinafter referred to as anhydride H3) 100 parts, the heated and stirred of 1 hour is carried out after 40 DEG C of reactions 3 hours at 70 DEG C。Confirm that Tricyclodecane Dimethanol is 1 below area % by GPC。Obtain the curing agent composition (Bb3) 120 parts comprising polycarboxylic acid compositions of the present invention。Gains are colourless liquid resin, by the GPC purity measured, and polycarboxylic acid compositions (Ab2；Following formula (4)) be 49 area %, methylhexahydrophthalic anhydride it is 51 area %。It addition, functional equivalent is 201g/eq.。

Formula (4):

Use Rotary Evaporators, at 100 to 150 DEG C, the methylhexahydrophthalic anhydride being present in excess is removed from curing agent composition (Bb3) 50 parts。This removal is, from the moment that methylhexahydrophthalic anhydride no longer flows out, passes into nitrogen 40 minutes, directly removes anhydride fully under heating reduced pressure。As a result of which it is, take out the polybasic carboxylic acid (Bb3a) 25 parts of the formula (1) of the present invention。

It is shaped as colourless semi-solid-state to solid-state resin。

The softening point (according to JISK-7234) of gained resin is 77.0 DEG C, and the melt viscosity at 150 DEG C is 0.24Pa s。

Embodiment b7 (curing agent composition Bb4)

In the flask possessing agitator, reflux condensing tube and agitating device, carry out nitrogen purging be simultaneously introduced Tricyclodecane Dimethanol 15 parts, methylhexahydrophthalic anhydride (new Japan Chemical (Co., Ltd.) manufacture；RikacidMH, hereinafter referred to as anhydride H3) 70 parts, hexamethylene-1,2,4-tricarboxylic acids-1, (Rhizoma Sparganii gas chemistry manufactures 2-acid anhydride；H-TMAn) 15 parts, 40 DEG C of reactions carry out the heated and stirred of 1 hour at 70 DEG C after 3 hours。Confirm that Tricyclodecane Dimethanol is 1 below area % by GPC。Obtain the curing agent composition (Bb4) 100 parts comprising polycarboxylic acid compositions of the present invention。Gains are colourless liquid resin, by the GPC purity measured, and polycarboxylic acid compositions (Ab3；Following formula (5)) to be 37 area %, hexamethylene-1,2,4-tricarboxylic acids-1,2-acid anhydride be 11 area %, methylhexahydrophthalic anhydride be 52 area %。It addition, functional equivalent is 171g/eq.。

Formula (5):

R=CH₃Or COOH

Embodiment b8 (curing agent composition Bb5)

In the flask possessing agitator, reflux condensing tube and agitating device, the curing agent composition (Bb3) 50 parts, the hexamethylene-1 that obtain it is simultaneously introduced in embodiment 6 what carry out nitrogen purging, 2,4-tricarboxylic acids-1, (Rhizoma Sparganii gas chemistry manufactures 2-acid anhydride；H-TMAn-S) 5 parts, carry out the stirring of 2 hours at 100 DEG C, obtain the curing agent composition (Bb5) of the present invention。The compositions obtained is colourless fluid composition。

Embodiment b9 (curing agent composition Bb6)

In the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced pentacyclopentadecane dimethanol 20 parts and 100 parts of anhydride (H3) what carry out nitrogen purging, after 40 DEG C of reactions 3 hours, carries out the heated and stirred of 1 hour at 70 DEG C。Confirm that pentacyclopentadecane dimethanol is 1 below area % by GPC。Obtain the curing agent composition (Bb6) 110 parts comprising polycarboxylic acid compositions of the present invention。The curing agent composition of gained is colourless fluid composition, by the GPC purity measured, and polycarboxylic acid compositions (Ab4；Following formula (6)) be 40 area %, methylhexahydrophthalic anhydride it is 60 area %。It addition, functional equivalent is 201g/eq.。

Formula (6):

Embodiment b10 (curing agent composition Bb7)

In the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced Tricyclodecane Dimethanol 10 parts and 100 parts of anhydride (H1), 50 DEG C of heated and stirred (confirming that Tricyclodecane Dimethanol is 1 below area % by GPC) carrying out 3 hours what carry out nitrogen purging。Obtain the curing agent composition (Bb7) 110 parts comprising polycarboxylic acid compositions of the present invention。Gains are colourless liquid resin, by the GPC purity measured, and polycarboxylic acid compositions (Ab1；Following formula (3)) be 27 area %, methylhexahydrophthalic anhydride it is 73 area %。It addition, functional equivalent is 185g/eq.。

Synthesis example b1 (compares and uses curing agent composition Bb8)

In the flask possessing agitator, reflux condensing tube and agitating device, at be simultaneously introduced Tricyclodecane Dimethanol 20 parts and the hexahydrophthalic anhydride that carry out nitrogen purging, (new Japan Chemical (Co., Ltd.) manufactures；RikacidHH) 100 parts, 50 DEG C of heated and stirred carrying out 3 hours, confirm that Tricyclodecane Dimethanol is 1 below area % by GPC。Obtain the curing agent composition (Bb8) 120 parts comprising polycarboxylic acid compositions compared。Gained curing agent composition is colourless fluid composition, by the GPC purity measured, and polycarboxylic acid compositions (A5；Following formula 7) be 48 area %, methylhexahydrophthalic anhydride it is 52 area %。It addition, functional equivalent is 200g/eq.。

Formula (7):

Synthesis example b2 (compares and uses curing agent composition Bb9)

In the flask possessing agitator, reflux condensing tube and agitating device, be simultaneously introduced ethylene glycol 10 parts and 100 parts of anhydride (H1) what carry out nitrogen purging, 40 DEG C carry out the reaction of 3 hours after carry out the heated and stirred of 1 hour at 70 DEG C。Confirm that raw material is 1 below area % by GPC。Obtain the curing agent composition (Bb9) 110 parts comprising polycarboxylic acid compositions compared。Gained curing agent composition is colourless fluid composition, by the GPC purity measured, and polycarboxylic acid compositions (Ab6；Following formula (8)) be the total amount of 25 area %, methylhexahydrophthalic anhydride and hexahydrophthalic anhydride it is 75 area %。It addition, functional equivalent is 185g/eq.。

Formula (8):

R=H or CH₃

Synthesis example b3 (compares and uses curing agent composition Bb10)

In the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced 1 what carry out nitrogen purging, 4-cyclohexanedimethanol 20 parts and 100 parts of anhydride (H1), 40 DEG C carry out the reaction of 3 hours after carry out the heated and stirred of 1 hour at 70 DEG C。Confirm that raw material is 1 below area % by GPC。Obtain the curing agent composition (Bb10) 120 parts comprising polycarboxylic acid compositions compared。Gained curing agent composition is colourless fluid composition, by the GPC purity measured, and polycarboxylic acid compositions (Ab7；Following formula 8) be the total amount of 53 area %, methylhexahydrophthalic anhydride and hexahydrophthalic anhydride it is 47 area %。It addition, functional equivalent is 200g/eq.。

Formula (9):

R=H or CH₃

Synthesis example b4 (compares and uses curing agent composition Bb11)

In the flask possessing agitator, reflux condensing tube and agitating device, be simultaneously introduced 1,6-hexanediol 20 parts and 100 parts of anhydride (H1) what carry out nitrogen purging, 40 DEG C carry out the reaction of 3 hours after carry out the heated and stirred of 1 hour at 70 DEG C。Confirm that raw material is 1 below area % by GPC。Obtain the curing agent composition (Bb11) 120 parts comprising polycarboxylic acid compositions compared。Gains are colourless liquid resin, by the GPC purity measured, and polycarboxylic acid compositions (Ab8；Following formula 10) be the total amount of 65 area %, methylhexahydrophthalic anhydride and hexahydrophthalic anhydride it is 35 area %。It addition, functional equivalent is 200g/eq.。

Formula (10):

R=H or CH₃

Synthesis example b5 (epoxy resin synthesis material alkadienes)

In the flask possessing agitator, reflux condensing tube, agitating device and Dean-Stark pipe, it is simultaneously introduced 1 what carry out nitrogen purging, 4-cyclohexane dicarboxylic acid 172 parts, 3-cyclohexene-1-methanol 448 parts, toluene 600 parts, p-methyl benzenesulfonic acid 4 parts, by the degree of decompression in regulation system in the way of 45 DEG C of backflows to remove the water generated, carry out the reaction of 12 hours simultaneously。After reaction terminates, reaction solution 10 weight % sodium hydrate aqueous solution 120 parts is carried out 3 washings, then it is repeatedly performed washing till waste water becomes neutrality with the water of 70 parts/time, use Rotary Evaporators under heating decompression, toluene and unreacted 3-cyclohexene-1-methanol are removed in distillation, thus obtain the diolefin compound 343 parts for liquid under room temperature。

Synthesis example b6 (epoxy resin-b2)

In the flask possessing agitator, reflux condensing tube and agitating device, carry out nitrogen purging be simultaneously introduced 15 parts of water, 12-tungstophosphoric acid 0.95 part, disodium hydrogen phosphate 0.78 part, two tallow alkyl dimethyl acetic acid ammonium 2.7 parts (ライオ Application ア Network ゾ manufacture；50 weight % hexane solutions, アカ De 2HT アセテト), the diolefin compound 118 parts that obtains in toluene 180 parts and synthesis example b5, and then stirring, thus obtain the liquid of emulsion state。By this solution warms to 50 DEG C, carrying out the stirring of fierceness, added 35 weight % aqueous hydrogen peroxide solution 70 parts with 1 hour simultaneously, former state stirs 13 hours at 50 DEG C。Confirm that reaction carries out to raw material crest disappearing by gas chromatogram。

Then, with in 1 weight % sodium hydrate aqueous solution and after, add 20 weight % sodium thiosulfate solution 25 parts, after stir 30 minutes standing。Organic layer is taken out after being separated into 2 layers, add 10 parts of silica gel (ワ U ゲ Le C-300) wherein, (NORIT manufactures activated carbon, CAPSUPER) 20 parts, bentonite (ホジュ Application manufactures, ベ Application ゲ Le SH) 20 parts, at room temperature stirring was filtered after 1 hour。With 100 parts of water, gained filtrate is carried out 3 times to wash, and remove toluene from the organic layer distillation obtained。Obtain the epoxy resin (EP-b2) 119 parts being main constituent for the below formula (11) of liquid under room temperature。The epoxide equivalent of gained epoxy resin is 217g/eq.。

Formula (11):

Embodiment b11, b12 (hardening resin composition), comparative example b2 (comparing with hardening resin composition)

Firming agent uses the curing agent composition (Bb2) of the present invention, (Bb3) that obtain in embodiment 3,6 and the comparison curing agent composition (Bb8) obtained in synthesis example b1；Epoxy resin uses epoxy resin (EP-1)；And use curing accelerator (C1), coordinate with the mixing ratio (weight portion) shown in following table b2, after carrying out the deaeration of 20 minutes, obtain the present invention or the hardening resin composition compared。

LED bright light is tested

It is filled in barrel after the hardening resin composition obtained in embodiment b11, b12 and comparative example 2 is implemented vacuum defoamation 20 minutes, uses accurate discharger to be poured into surface mounting LED (the SMD type 5mm φ of the light-emitting component being equipped with emission wavelength 465nm；Scheduled current is 30mA) in。Then, solidify with predetermined condition of cure, thus obtain bright light test LED。Bright light test is to carry out under the electric current of 2 times of scheduled current 30mA。Detailed conditions is as follows。As the project of mensuration, use integrating sphere to measure the bright light forward and backward illumination of 200 hours, and calculate the conservation rate of the illumination of test LED。Show the result in table b2。

Bright light detailed conditions

Emission wavelength: center emission wavelength, 465nm

Type of drive: constant current behavior, 60mA (light-emitting component scheduled current is 30mA) connect 3 be bright light simultaneously

Drive environment: 85 DEG C, bright light in 85% damp and hot machine

Evaluate: bright light illumination after 200 hours and its illumination conservation rate, and the painted * of chip

(* is evaluated with visualization, when being caused deterioration by bright light test, chip produces painted, thus has illumination and declines the tendency of aggravation。)

Table b2

Can be clear and definite by the above results, the polycarboxylic acid compositions that comparison curing agent composition (Bb8) comprises only comprises the R in above formula (1) and is the compound of hydrogen atom, compare with for curing agent composition (Bb8) for such, illumination keeps rate variance, it can be seen that chip painted。On the other hand, the polycarboxylic acid compositions that the hardening resin composition of the present invention comprises is included on R and introduces the compound having methyl, for the hardening resin composition of such present invention, illumination after initial stage illumination and bright light test is all excellent, painted also few on chip, such that it is able to obtain the solidfied material that resistance to deterioration is strong, the LED suitable in industrial applications therefore can be manufactured。

Embodiment b13, b14, b15, b16, b17, comparative example b3, b4, b5

Firming agent uses the curing agent composition (Bb9), (Bb10), (Bb11) that obtain in the curing agent composition (Bb3) of the present invention, (Bb4), (Bb5), (Bb6), (Bb7) and synthesis example b2, b3, the b4 obtained in embodiment b6, b7, b8, b9, b10；Epoxy resin uses the epoxy resin (EP-b2) obtained in epoxy resin (EP-1), synthesis example b6；And (Japan's synthesis chemistry manufactures to use curing accelerator；ヒシ U リ Application PX4MP), coordinate with the mixing ratio (weight portion) shown in Table 3 below, after carrying out the deaeration of 20 minutes, obtain the present invention or the hardening resin composition compared。

(thermal endurance test)

After the hardening resin composition obtained in embodiment b13 to b17, comparative example b3 to b5 is implemented vacuum defoamation 20 minutes, it is poured into lentamente in the cofferdam made on the glass substrate with heat resistant adhesive tape and obtains 30mm × 20mm × height 1mm, obtain the absorbance test film of thickness 1mm so that the condition of 150 DEG C × 1 hour after the precuring of 120 DEG C × 3 hours makes this casting solidify。

Use these test films, in the baking oven of 150 DEG C, place 96 hours forward and backward absorbancies (measuring wavelength: 400nm) by spectrophotometric determination, and calculate the conservation rate of absorbance。Show the result in table b3。

Table b3

From the above results, comprise the hardening resin composition of the polycarboxylic acid compositions of the present invention, there is the patience to heat deterioration and its conservation rate is high, therefore can be suitable for optical applications。

Embodiment a

In the flask possessing agitator, reflux condensing tube and agitating device, in 1,3,4-cyclohexanetricarboxylic acid-3 that are simultaneously introduced carrying out nitrogen purging, (H-TMA, Rhizoma Sparganii gas chemistry manufactures 4-acid anhydride；H2) 118.9 parts, methylhexahydrophthalic anhydride (new Japan Chemical (Co., Ltd.) manufacture；RikacidMHH3) 403.2 parts, butanone 349.9 parts, after being warming up to 40 DEG C, with the Tricyclodecane Dimethanol 294.4 parts adding pre-temperature to 70 DEG C for 30 minutes, stir at 40 DEG C 30 minutes, then stir 4 hours at 70 DEG C while stirring。Use Rotary Evaporators, at 100 to 150 DEG C, from gained reactant liquor, remove solvent, obtain the polycarboxylic acid compositions (x) 816 parts of the present invention。It is shaped as colourless solid resin。Functional equivalent is 272g/eq.。

The softening point (according to JISK-7234) of gained resin is 99.8 DEG C, and the melt viscosity at 150 DEG C is 0.92Pa s。

* melt viscosity

Melt viscosity in cone at 150 DEG C-plate method

Measure machinery: cone-plate (ICI) high-temperature viscosimeter

(RESEARCHEQUIPMENT (LONDON) LTD. manufacture)

Tapered number: 3 (measurement range 0 to 2.00Pa s)

Hereinafter, it is measured with similarity condition。

Embodiment b

Use Rotary Evaporators, at 100 to 150 DEG C, the methylhexahydrophthalic anhydride being present in excess is removed (from the moment that methylhexahydrophthalic anhydride no longer flows out from curing agent composition (B4) 50 parts, it is passed directly into nitrogen 40 minutes under heating reduced pressure, anhydride can be removed fully), thus take out the polycarboxylic acid compositions (x2) 24 parts of the present invention。It is shaped as colourless solid resin。

The softening point (according to JISK-7234) of gained resin is 72.4 DEG C, and the melt viscosity at 150 DEG C is 0.38Pa s。

Embodiment c

In the flask possessing agitator, reflux condensing tube and agitating device, in 1,3,4-cyclohexanetricarboxylic acid-3 that are simultaneously introduced carrying out nitrogen purging, (H-TMA, Rhizoma Sparganii gas chemistry manufactures 4-acid anhydride；H2) 162 parts, methylhexahydrophthalic anhydride (new Japan Chemical (Co., Ltd.) manufacture；RikacidMHH3) 787 parts, butanone 400 parts, after being warming up to 40 DEG C, with the Tricyclodecane Dimethanol 540 parts adding pre-temperature to 70 DEG C for 30 minutes, stir at 40 DEG C and stir 4 hours for 30 minutes, then 70 DEG C while stirring。Use Rotary Evaporators, at 100 to 150 DEG C, from gained reactant liquor, remove solvent, thus obtain the polycarboxylic acid compositions (x3) 1489 parts of the present invention。It is shaped as colourless solid resin。Functional equivalent is 271g/eq.。

The softening point (according to JISK-7234) of gained resin is 80.6 DEG C, and the melt viscosity at 150 DEG C is 0.43Pa s。

Synthesis example A

In the flask possessing agitator, reflux condensing tube and agitating device, it is simultaneously introduced 10 parts of water, cyclohexenyl methyl cyclohexene carboxylate ester 110 parts, toluene 140 parts, 12-tungstophosphoric acid 1 part, sodium tungstate 1.5 parts, disodium hydrogen phosphate 1.5 parts, trioctylphosphine ammonium acetate 50% xylene solution 1.5 parts what carry out nitrogen purging, by this solution warms to 45 DEG C, 35 weight % aqueous hydrogen peroxide solution 110 parts is added with 20 minutes, then, it is maintained at 45 ± 5 DEG C and stirs 12 hours。

Then, with in 1 weight % sodium hydrate aqueous solution and after, add 20 weight % sodium thiosulfate solution 25 parts and stir and stand after 30 minutes。Taking out organic layer after being separated into 2 layers, (aginomoto fine chemistry manufactures to add activated carbon wherein；CP2) 5 parts, montmorillonite (Network ニミネ work manufacture；Network ニピア F) 5 parts, at room temperature stirring was filtered after 3 hours。With 100 parts of water, gained filtrate being carried out 3 washings, and removes toluene from the organic layer distillation obtained, obtain with 3,4-epoxycyclohexylmethyl-3,4-expoxycyclohexyl carboxylate is the epoxy resin (EP5) 111 parts of main constituent。The epoxide equivalent of gained epoxy resin is 130g/eq.。Viscosity at 25 DEG C is 211mPa s (E type viscometer)。

Embodiment A, B, C, D, E, F, G, H, I, J, K, L

Epoxy resin uses epoxy resin (EP2), epoxy resin (EP5)；Firming agent uses curing agent composition (Bb3, Bb4, Bb5, x1, x3), anhydride (H3)；Curing accelerator uses seasonSalt (C2)；Additive uses (L1) (M1), light stabilizer, and (ADEKA manufactures；LA-62, hereinafter referred to as L2)；Phosphorus compound uses tricresyl phosphite alkane ester, and (ADEKA manufactures；アデカスタ Block 3010, hereinafter referred to as M2), alkyl phosphoric acid zinc (KingIndustries manufacture；XC-9206, hereinafter referred to as M3), coordinate with the mixing ratio (weight portion) shown in following Table A, after carrying out the deaeration of 20 minutes, obtain the present invention or the hardening resin composition compared。The hardening resin composition obtained carries out tests below。Result is illustrated in together following Table A。

(Reflow Soldering, the test of LED bright light)

The hardening resin composition obtained in embodiment and comparative example is filled in barrel and uses accurate discharger to be poured in surface mounting LED encapsulation (internal diameter 4.4mm, outer wall height 1.25mm) square for external diameter 5mm of the chip being equipped with center luminescence ripple 465nm。This casting is put into heating furnace, carries out 120 DEG C, 1 hour, the cured of then 150 DEG C, 3 hours, obtain LED encapsulation。For gained LED, photo detector is used to be measured simply the illumination before and after Reflow Soldering。(under shading, make it luminous with the electric current of scheduled current 30mA the LED obtained, with photo detector (visible ray photodiode (photodiodevisiblelight), BS500B, シャプ manufactures) light, using the current value in this flowing as the yardstick of illumination)。Mensuration is after LED is just sealed and illumination after Reflow Soldering test is measured, and confirms its difference。Show the result in Table A。

It addition, Reflow Soldering test uses high temperature observation device, simulation ground imitates Reflow Soldering。Device, condition are as described below。

Device: high temperature observation device (SMTScopeSK-5000；Adret Jinggong Co., Ltd manufactures)

Temperature conditions: be warming up to 150 DEG C with 2 DEG C/sec by 25 DEG C, then at 150 DEG C keep 2 minutes, then 2 DEG C/sec be warming up to 260 DEG C and keep 10 seconds after, be cooled to room temperature with 1.3 DEG C/sec。

Table A

By result above it can be seen that have the curing agent composition of the polycarboxylic acid compositions of the present invention, high temperature during if exposed to Reflow Soldering can also keep illumination with high conservation rate, there is high optical characteristics。

Industrial applicability

The polycarboxylic acid compositions of the present invention is excellent to the ability to cure of epoxy resin, can be suitable as the firming agent of epoxy resin。Additionally, this polycarboxylic acid compositions coordinated in the epoxy, volatilization in the temperature range being generally used for cured epoxy resin is few, can stably realize the target capabilities of solidfied material, such as high transparency and heat durability (such as: reflux-resisting welded property, LED long-term bright light in illumination conservation rate, light absorbance conservation rate etc.), therefore extremely useful at the seal aspect of LED。

Claims

1., for a compositions for hardener for epoxy resin, it comprises the polybasic carboxylic acid represented by following formula (1),

In formula, R represents the alkyl of carbon number 1 to 6 independently of one another；P represents the divalent linking group defined by following (a):

Any one in a divalent group that () is represented by following formula (a1),

(a1)

2. the compositions for hardener for epoxy resin as claimed in claim 1, wherein, (a) linking group defined is the divalent group obtained after removing 2 hydroxyls from 2,4-diethyl-1,5-PD。

3. the compositions for hardener for epoxy resin as claimed in claim 1, wherein, the R in formula (1) is methyl。

4. the compositions for hardener for epoxy resin as claimed in claim 1, wherein, the compositions for hardener for epoxy resin comprises: polybasic carboxylic acid that at least one is represented by formula (1) and can by methyl substituted C₄To C₇Ring-type two, three or tetracarboxylic anhydride。

5. the compositions for hardener for epoxy resin as claimed in claim 4, wherein it is possible to by methyl substituted C₄To C₇Ring-type two, three or tetracarboxylic anhydride, for can by methyl substituted hexamethylene two or tricarboxylic acid anhydride。

6. a hardener for epoxy resin, its polybasic carboxylic acid comprising the formula (1) described in claim 1 or the compositions for hardener for epoxy resin described in claim 4。

7. hardener for epoxy resin as claimed in claim 6, it is for comprising:

Polybasic carboxylic acid, wherein, the divalent linking group represented by P in formula (1) is the linking group defined by (a) and the linking group that defined by (a) is the divalent group described in following (1), and

Polycarboxylic acid compositions,

(1) divalent group:

(2) anhydride:

8. a hardening resin composition, it comprises the compositions for hardener for epoxy resin described in claim 1 or the firming agent described in claim 6 and epoxy resin。

9. hardening resin composition as claimed in claim 8, wherein, epoxy resin is alicyclic epoxy resin。

10. hardening resin composition as claimed in claim 9, wherein, firming agent is the firming agent described in claim 7。

11. a solidfied material, it is the solidfied material of the hardening resin composition described in claim 8。

12. a manufacture method for the polybasic carboxylic acid represented by formula (1) described in claim 1, wherein, make dihydroxylic alcohols and (c) reaction of following (a),

A () has any one in the dihydroxylic alcohols of the structure represented by following formula (a1),

(a1)

In formula, the * mark of the end of each structure represents and is bonded with hydroxyl；

(c) anhydride, it is the mixture of methylhexahydrophthalic anhydride or methylhexahydrophthalic anhydride and hexahydrophthalic anhydride or methylhexahydrophthalic anhydride and hexamethylene-1,2, the mixture of 4-tricarboxylic acid anhydride or methylhexahydrophthalic anhydride, hexahydrophthalic anhydride and hexamethylene-1, the mixture of 2,4-tricarboxylic acid anhydrides。

13. the manufacture method of polybasic carboxylic acid as claimed in claim 12, wherein, it is calculated as the ratio of 0.001 to 2 equivalent relative to anhydride group 1 equivalent with the hydroxyl equivalent of dihydroxylic alcohols, at reaction temperature 40 to 150 DEG C, makes the dihydroxylic alcohols of (a) and the anhydride reaction of (c)。

14. the manufacture method of polybasic carboxylic acid as claimed in claim 13, wherein, the anhydride of (c) is the mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride。

15. the manufacture method of polybasic carboxylic acid as claimed in claim 13, wherein, dihydroxylic alcohols is 2,4-diethyl-1,5-PD。

16. the manufacture method of polybasic carboxylic acid as claimed in claim 13, it includes the step making 2,4-diethyl-1,5-PD and methylhexahydrophthalic anhydride react。

17. the polybasic carboxylic acid represented by following formula (1),

Any one in a divalent group that () is represented by following formula (a1),

(a1)

18. polybasic carboxylic acid as claimed in claim 17, wherein, (a) the divalent linking group defined is the alkylidene obtained after removing 2 hydroxyls from 2,4-diethyl-1,5-PD。

19. polybasic carboxylic acid as claimed in claim 17, wherein, the R in formula (1) is methyl。