JP2009067908A - Curable composition for laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for a laminate, exhibiting sufficient peel strength, excellent heat resistance and hygroscopicity. <P>SOLUTION: The curable composition for the laminate contains (A) a curing type main agent containing a compound represented by general formula (1) (wherein, at least two of Z<SP>1</SP>to Z<SP>24</SP>are groups having polymerizable functional groups), and (B) a curing agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable composition for a laminate capable of producing a laminate having excellent characteristics.

  Conventionally, what consists of various raw materials etc. is known as a laminated board processed into a printed wiring board etc. FIG. As a specific example of such a laminate, a predetermined number of prepregs prepared by impregnating a resin such as an epoxy resin into a substrate such as a glass cloth and drying, a metal foil such as a copper foil is laminated as necessary. A product produced by heating and press-molding a laminated body further laminated on one side or both sides is known.

  Such laminated boards are required to improve various characteristics such as heat resistance and workability in response to the trend of high-density mounting and high integration of printed wiring boards. Among the required properties, heat resistance can be cited as an important property, and it has been studied to increase the heat resistance of a general epoxy resin as a resin constituting a laminated board.

  In order to improve the heat resistance of the epoxy resin, the polyfunctional epoxy resin is cured using dicyandiamide, DDS, DDM, or alkylated or halogenated DDM is used as a curing agent, or the epoxy resin is an imide resin. Modification has been proposed. It has also been proposed to use a phenolic resin such as a phenol novolac resin, a cresol novolak resin, or a bisphenol A type novolak resin as a curing agent.

  However, in the above proposal, although the heat resistance of the epoxy resin is good, there is a tendency that the hygroscopicity and the solder heat resistance after moisture absorption are insufficient and the product life of the prepreg is shortened. In order to avoid the occurrence of such problems, a phenolic resin composition for laminates in which a phenolic curable brominated epoxy resin is blended with a phenolic resin varnish (see, for example, Patent Document 1) is disclosed. Also disclosed is an epoxy resin composition using a compound having two or more phenolic hydroxyl groups in one molecule and an aromatic amine compound having two or more amino groups in one molecule together with dicyandiamide. (For example, refer to Patent Document 2).

  However, even with the resin compositions disclosed in Patent Documents 1 and 2, etc., the heat resistance is still not sufficient. There is also room for improvement in properties such as low hygroscopicity and peel strength.

JP-A-4-222816 Japanese Patent Laid-Open No. 5-51436

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is to produce a laminate having sufficient peel strength and excellent heat resistance and hygroscopicity. The object is to provide a curable composition for a laminate.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have achieved the above-mentioned problems by using calixarene compound derivatives whose molecular structure is represented by a specific general formula as a curable main agent. As a result, the present invention has been completed.

  That is, according to this invention, the curable composition for laminated boards shown below is provided.

  [1] A curable composition for a laminate comprising (A) a curable main agent containing a compound represented by the following general formula (1), and (B) a curing agent.

In the general formula (1), R ^{1 to} R ⁶ each independently represent a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and X ^{1 to} X ¹² each independently represent 1 carbon atom. Substituted or unsubstituted alkyl group having 10 to 10 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, substituted or unsubstituted carbon group having 7 to 10 carbon atoms An aralkyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and Z ^{1 to} Z ²⁴ are groups having a hydrogen atom or a polymerizable functional group, independently of each other; , A group having an alkali-soluble group, a substituted alkyl group having 1 to 8 carbon atoms in the alkyl chain, or a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms formed by bonding two adjacent Z's (provided that , ^Z 1 ~Z At least two of the ⁴ is a group having a polymerizable functional group), q ¹ to q ¹² are independently of each other, an integer of 0 or 1.

  [2] The curable composition for laminates according to [1], wherein the polymerizable functional group is a substituted or unsubstituted glycidyl group.

  [3] The curable composition for laminates according to [1] or [2], wherein the (B) curing agent includes a compound represented by the following general formula (2).

In the general formula (2), R ^{1 to} R ⁶ each independently represent a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and X ^{1 to} X ¹² each independently represent 1 carbon atom. Substituted or unsubstituted alkyl group having 10 to 10 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, substituted or unsubstituted carbon group having 7 to 10 carbon atoms An aralkyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group; q ^{1 to} q ¹² each independently represents an integer of 0 or 1;

  [4] (A) Hydrogen of the phenolic hydroxyl group of a compound having a phenolic hydroxyl group obtained by condensing a compound represented by the following general formula (3) and a compound represented by the following general formula (4) A curable composition for laminates, comprising a curable main agent comprising a compound in which at least two of the atoms are substituted with a group having a polymerizable functional group, and (B) a curing agent.

  In the general formula (3), X is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, q is an integer of 0 or 1 Indicates.

  In the general formula (4), R represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms.

  [5] The curable composition for laminated boards according to [4], wherein R in the general formula (4) is a propylene group.

  The curable composition for laminated boards of the present invention has an effect that a laminated board having sufficient peel strength and exhibiting excellent heat resistance and hygroscopicity can be produced.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

  One embodiment of the curable composition for laminated boards of the present invention contains (A) a curable main agent containing the compound represented by the general formula (1), and (B) a curing agent. . The details will be described below.

((A) Main agent)
The main component (A) contained in the curable composition for laminated boards of the present invention contains a compound represented by the following general formula (1) (so-called “calixarene compound derivative”), and (B) It is a component that can be cured by a curing agent. Note that (A) the main agent may contain a curable resin material that can be used to form a laminate including an epoxy resin. However, (A) the main agent is preferably substantially composed of a compound represented by the following general formula (1).

In the general formula (1), R ^{1 to} R ⁶ each independently represent a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and X ^{1 to} X ¹² each independently represent 1 carbon atom. Substituted or unsubstituted alkyl group having 10 to 10 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, substituted or unsubstituted carbon group having 7 to 10 carbon atoms An aralkyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and Z ^{1 to} Z ²⁴ are groups having a hydrogen atom or a polymerizable functional group, independently of each other; , A group having an alkali-soluble group, a substituted alkyl group having 1 to 8 carbon atoms in the alkyl chain, or a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms formed by bonding two adjacent Z's, q ^{1 ~q 12} is Independently of one another, an integer of 0 or 1.

In the general formula (1), at least 2, preferably 8 or more, more preferably 16 or more, particularly preferably 24 (all) of Z ^{1 to} Z ²⁴ have a polymerizable functional group. It is. The present invention in which the compound represented by the general formula (1) is contained in the main agent when at least two of Z ^{1 to} Z ^{24 in} the general formula (1) are groups having a polymerizable functional group. This curable composition for laminates exhibits excellent properties as a curable composition. Further, the compound represented by the general formula (1) preferably has one or more polymerizable functional groups in one aromatic ring, and has two polymerizable functional groups in one aromatic ring. Is more preferable.

  Specific examples of the polymerizable functional group include a group having a polymerizable unsaturated structure and a group having a cyclic ether structure. More specifically, a vinyl group, a vinylidene group, an acryloyl group, a methacryloyl group, a substituted or unsubstituted glycidyl group, a substituted or unsubstituted oxetanyl group, a substituted or unsubstituted spiro orthoester group, and the like can be given. Among these, the polymerizable functional group is preferably a substituted or unsubstituted glycidyl group.

In the general formula (1), the group represented by Z ^{1 to} Z ²⁴ is preferably a group having an alkali-soluble group. Specific examples of the alkali-soluble group include a carboxyl group, an amino group, a sulfonamide group, a sulfonic acid group, and a phosphoric acid group.

In the general formula (1), at least one of the groups represented by Z ^{1 to} Z ²⁴ is preferably a substituted alkyl group having 1 to 8 carbon atoms in the alkyl chain. For example, by using an alkyl group as a spacer and attaching a functional group as described above to the tip, the degree of freedom of the functional group is improved and the reactivity is improved. Or the derivative | guide_body which has the substituted alkyl group substituted by the substituent which can add or substitute the above functional groups as mentioned above is also preferable. Furthermore, derivatives having a substituted alkyl group in which the functional group or substituent as described above is protected by a protecting group are also preferred.

  In the general formula (1), it is also preferable that two adjacent Zs are bonded to form a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms. By adopting such a structure, the conformation can be firmly fixed, and it is also useful as an inclusion compound that includes a specific compound.

In the general formula (1), the substituents (X ^{1 to} X ¹² ) in one aromatic ring may be omitted, but it is also preferable to have various substituents depending on the purpose. X ^{1 to} X ¹² in the general formula (1) are preferably each independently a hydrogen atom or a methyl group.

In the general formula (1), R ^{1 to} R ⁶ are preferably an alkylene group having 3, 5, 7 or 8 carbon atoms from the viewpoint that the basic skeleton of the cyclic body can be easily formed. Furthermore, when all of R ^{1 to} R ⁶ are straight-chain alkylene groups having 3 carbon atoms, it is more preferable because the basic skeleton of the cyclic body can be formed with a very high yield.

  (A) In the case where an epoxy resin is contained in the main agent, as the epoxy resin, any conventionally used resin component such as an electrical laminate can be used. Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, diaminodiphenyl ether type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy. Examples thereof include trifunctional epoxy resins such as resins, isocyanurate type epoxy resins and triphenylmethane type epoxy resins; tetrafunctional type epoxy resins; halides thereof and the like. In addition, it is preferable that the epoxy equivalent of an epoxy resin is 150-1000 g / eq. These epoxy resins can be used individually by 1 type or in combination of 2 or more types.

((B) curing agent)
The curable composition for laminated boards of the present invention contains (B) a curing agent. The curable composition for laminated boards of the present invention contains a curable (A) main agent containing the above-mentioned compound (calixarene compound derivative) having a group having a polymerizable functional group in its molecular structure. Yes. Therefore, the main component (A) can be cured by including the curing agent (B).

  (B) As a hardening | curing agent, what is generally used as a hardening | curing agent for one-component or two-component epoxy resins can be used. Specific examples of (B) curing agents include amine compounds, imidazole compounds, modified amine compounds, modified imidazole compounds, phenolic compounds, and phenolic resins.

  Specific examples of the amine compound include dicyandiamide; aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and diethylaminopropylamine; aromatic polyamines such as m-xylenediamine and diaminodiphenylmethane; alicyclic polyamines such as isophoronediamine and mensendiamine. A polyamide or the like.

  Specific examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

  Specific examples of the modified amine compound include an epoxy compound-added polyamine obtained by adding an amine compound to an epoxy compound. Examples of the modified imidazole compound include an imidazole adduct obtained by adding an imidazole compound to an epoxy compound.

  Specific examples of the phenol compound include bisphenol A, pyrogallol catechol, resorcin, cresol, allylated bisphenol A, and the like. Specific examples of phenolic resins include novolak type phenolic resins, alkylphenolic resins, benzyl ether type phenolic resins, phenol aralkyl resins, alkenyl group-containing phenolic resins, allyl group-containing phenolic resins, poly-P-vinylphenol, and the like. be able to.

  (B) Use of a compound represented by the following general formula (2) (calixarene compound) as a curing agent has a better peel strength, and further exhibits excellent heat resistance and moisture absorption. Is preferable because it can be manufactured.

In the general formula (2), R ^{1 to} R ⁶ each independently represent a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and X ^{1 to} X ¹² each independently represent 1 carbon atom. Substituted or unsubstituted alkyl group having 10 to 10 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, substituted or unsubstituted carbon group having 7 to 10 carbon atoms An aralkyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group; q ^{1 to} q ¹² each independently represents an integer of 0 or 1;

  The aromatic ring in the general formula (2) is a monosubstituted or unsubstituted resorcinol ring. When the aromatic ring is a monosubstituted or unsubstituted resorcinol ring, the conformation can be easily fixed, and the functionalization by chemical modification with respect to the hydroxyl group is facilitated.

In the general formula (1), the substituents (X ^{1 to} X ¹² ) in one aromatic ring may be omitted, but it is also preferable to have various substituents depending on the purpose. X ^{1 to} X ¹² in the general formula (1) are preferably each independently a hydrogen atom or a methyl group.

In the general formula (1), R ^{1 to} R ⁶ are preferably an alkylene group having 3, 5, 7 or 8 carbon atoms from the viewpoint that the basic skeleton of the cyclic body can be easily formed. Furthermore, when all of R ^{1 to} R ⁶ are straight-chain alkylene groups having 3 carbon atoms, it is more preferable because the basic skeleton of the cyclic body can be formed with a very high yield.

(Other ingredients)
In the curable composition for laminates of the present invention, if necessary, other components can be blended as long as the effects of the present invention are not impaired. Examples of other components that can be blended include a curing accelerator, a polymerization initiator, and a solvent.

  Specific examples of the curing accelerator include conventionally known imidazole compounds and amine compounds as curing accelerators for epoxy resins.

  Specific examples of the polymerization initiator include benzoin, benzoin ethyl ether, dibenzyl, isopropyl benzoin ale, benzophenone, Michler's ketone chlorothioxanthone, dodecyl thioxanthone, dimethylthioxanthone, acetophenone diethyl ketal, benzyl dimethyl ketal, α-hydroxycyclohexyl phenyl ketone, etc. Photopolymerization initiators; thermal polymerization initiators and the like.

  Specific examples of the solvent include methyl ethyl ketone, acetone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, methanol, ethanol, toluene, xylene, dimethylformamide (DMF), dimethylacetamide (DMAc) and the like. . In addition, when using a solvent, it is preferable to mix | blend so that solid content concentration may be 50-70 mass%.

(Method for producing calixarene compound)
The compound (calixarene compound) having a phenolic hydroxyl group represented by the general formula (2) is represented by the following general formula (3) as described in, for example, International Publication No. 2005/075398. Can be produced by condensing the compound represented by the following general formula (4).

  In the general formula (3), X is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, q is an integer of 0 or 1 Indicates.

  In the general formula (4), R represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms.

The compound represented by the general formula (3) is monosubstituted or unsubstituted dihydroxybenzene. Moreover, X and q in the general formula (3) respectively correspond to the ^X 1 ^{to X 12} and ^q 1 ^{to q 12} in the general formula (2). Specific examples of the compound represented by the general formula (3) include resorcinol, 2-methylresorcinol, 2-butylresorcinol and the like. Of these, resorcinol and 2-methylresorcinol are preferable.

The compound represented by the general formula (4) is a dialdehyde compound. R in the general formula (4) corresponds to R ^{1 to} R ⁶ in the general formula (2). Specific examples of the compound represented by the general formula (4) include 1,5-pentane dial, 1,7-heptane dial, 1,9-nonane dial, 1,10-decandial, and the like. . In addition, it is preferable that R in the said General formula (4) is a propylene group.

  Condensation of the compound represented by the general formula (3) (hereinafter also referred to as “compound (A)”) and the compound represented by the general formula (4) (hereinafter also referred to as “compound (B)”) In the process, the molar ratio of these compounds is not particularly limited, but from the viewpoint of yield, the value (molar ratio) of compound (B) / compound (A) is 0.05 to 0.85. Is preferable, 0.075 to 0.6 is more preferable, and 0.1 to 0.3 is particularly preferable. Further, the monomer concentration in the reaction solution (the total concentration of the compound (A) and the compound (B)) is not particularly limited, but is preferably 2 mol / L or more from the viewpoint of yield, and 4 mol / L. More preferably, it is more preferably 4 to 10 mol / L. The reaction proceeds sequentially by dehydrating and condensing the compound (A) and the compound (B) in an appropriate solvent in the presence of a catalyst, and finally a calixarene compound can be obtained.

(Method for producing calixarene compound derivative)
The calixarene compound derivative represented by the general formula (1) is represented by the general formula (2) obtained by the above-described method as described in, for example, International Publication No. 2005/075398. A hydrogen atom of a phenolic hydroxyl group in a compound having a phenolic hydroxyl group (calixarene compound), a group having a polymerizable functional group, a group having an alkali-soluble group, or a substituted alkyl group having 1 to 8 carbon atoms in the alkyl chain It can manufacture by substituting with. In addition, substitution of the hydrogen atom of a phenolic hydroxyl group can be performed by a conventionally well-known method. For example, a compound having a reactivity with a phenolic hydroxyl group such as a halogen or an epoxy group and a desired functional group such as a polymerizable functional group is present in a solvent such as THF in the presence of a catalyst such as triethanolamine. A calixarene compound derivative can be obtained by reacting with the compound represented by the general formula (2).

(Laminate production method)
Next, an example of a method for producing a laminated board using the curable composition for laminated boards according to an embodiment of the present invention will be described. Since the curable composition for laminated boards of this embodiment is apply | coated or impregnated at a base material, it is normally used in the state (liquid state) diluted with the solvent. As the solvent to be diluted, the above-mentioned solvents can be used.

After impregnating the curable composition for laminates on a suitable substrate such as glass cloth, glass paper, kraft paper, linter paper, cloth, etc., it is dried for about 3 to 10 minutes at 120 to 180 ° C. in a dryer. By doing so, a prepreg in a B-stage (semi-cured) state can be obtained. If the obtained prepreg is heated and pressed under conditions of 150 to 200 ° C. and 10 to 50 kg / cm ^2, a laminate can be produced. In addition, if the metal foil for printed wiring is affixed, the metal foil tension laminated board for printed wiring can also be manufactured. Specific examples of the metal foil that can be attached include copper foil, aluminum foil, and stainless steel foil. A predetermined number of metal foils and a prepreg may be laminated and formed. In addition, when manufacturing a multilayer laminate using an epoxy resin material, the surface of the inner layer copper foil is generally chemically treated (blackened) to form copper oxide. Is preferably 150 to 180 ° C.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

(Synthesis Example 1)
2.20 g (20 mmol) of resorcinol was dissolved in 4.5 mL of ethanol and 1.5 mL of hydrochloric acid was added. The mixture was ice-cooled to 5 ° C. with stirring, and 0.40 g (2 mmol) of a 50% aqueous solution of glutaraldehyde was slowly added dropwise. Then, it heated at 80 degreeC for 48 hours, and obtained the yellow suspension. The obtained suspension was poured into methanol, and the produced precipitate was filtered and washed with methanol three times. The obtained precipitate was dried under reduced pressure at room temperature for 24 hours to obtain a powdery pale yellow solid (compound (1)). The structure of the obtained compound (1) was confirmed by MALDI-TOF-MS, IR, and ¹ H-NMR. The results of the structure confirmation are shown below. The structure of the obtained compound (1) is shown in the following formula (5). In the following formula (5), symbols (af) attached to the respective hydrogen atoms correspond to the symbols of hydrogen in ¹ H-NMR data.

Mass spectrometry (MALDI-TOF-MS): It was shown that only a compound with a molecular weight of 1705.86 was obtained.
Yield: 0.43 g (Yield: 79%)
IR (film method, cm ⁻¹ ): 3406 (ν _OH ); 2931 (ν _C—H ); 1621, 1505, 1436 (ν _{C = C (aromatic)} )
¹ H-NMR (500 MHz, solvent; CDCl ₃ , internal standard; TMS): δ (ppm) = 0.86 to 2.35 (b, 32.0H, H ^a , H ^b ), 3.98 to 4. ^{22 (m, 4.0H, H c} ), 6.09~7.42 (m, 8.0H, aromaticH d, H e), 8.65~9.56 (m, 8.0H, OH f)

(Synthesis Example 2)
Compound (1) 0.30 g (0.18 mmol, OH equivalent 4.22 mmol) obtained in “Synthesis Example 1” and 0.07 g (0.21 mmol) of tetrabutylammonium bromide (TBAB) were dissolved in 9 mL of NMP. After that, 0.25 g (10.6 mmol) of sodium hydride was added and stirred at room temperature for 1 hour. After salt formation, 1.18 g (12.7 mmol) of 3-chloro-1,2-propylene oxide was further added, and the mixture was stirred at 80 ° C. for 48 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate, washed three times with distilled water, and the organic phase was dried over anhydrous magnesium sulfate. The desiccant was filtered off and concentrated. Reprecipitation was performed using chloroform as a good solvent and n-hexane as a poor solvent to obtain a white powder solid (compound (2)). The structure of the obtained compound (2) was confirmed by IR, ¹ H-NMR, and MALDI-TOF-MS, and it was found that the etherification rate of the obtained compound (2) was 100%. The structure of the obtained compound (2) is shown in the following formula (6).

Example 1
The compound (1) obtained in “Synthesis Example 1” and the compound (2) obtained in “Synthesis Example 2” were mixed at a predetermined ratio, and then mixed with a mixed solvent of methyl cellosolve and DMF (mass ratio = 1: 1). Dissolved, stirred at 40 ° C. for 30 minutes, and then cooled to 20 ° C. A predetermined amount of 2-ethyl-4-methyl-imidazole was added as a curing accelerator to prepare a curable composition. A glass cloth was impregnated with the prepared curable composition to obtain a prepreg, and a 1.6 mm double-sided copper foil-clad laminate was produced using the obtained prepreg. The copper foil peel strength, glass transition temperature (Tg), and moisture absorption rate of the manufactured laminate were measured and evaluated. As a result, good results were obtained for all, and it was possible to produce a laminate having a well-balanced heat resistance.

  If the curable composition for laminated boards of this invention is used, while having sufficient peel strength, the laminated board which shows the outstanding heat resistance and moisture absorption can be manufactured.

Claims (5)

(A) a curable main agent containing a compound represented by the following general formula (1);
(B) The curable composition for laminated boards containing a hardening | curing agent.

(In the general formula (1), R ^{1 to} R ⁶ each independently represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and X ^{1 to} X ¹² each independently represents a carbon number. A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted group having 7 to 10 carbon atoms An aralkyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, Z ^{1 to} Z ²⁴ each independently have a hydrogen atom and a polymerizable functional group. A group having an alkali-soluble group, a substituted alkyl group having 1 to 8 carbon atoms in the alkyl chain, or a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms formed by bonding two adjacent Z's ( ^{However, Z} 1 ~ At least two of the ^24, a group having a polymerizable functional ^group), q 1 ^{to q 12} are independently of each other, an integer of 0 or 1)   The curable composition for laminated boards according to claim 1, wherein the polymerizable functional group is a substituted or unsubstituted glycidyl group. The curable composition for laminates according to claim 1 or 2, wherein the (B) curing agent contains a compound represented by the following general formula (2).

(In the general formula (2), R ^{1 to} R ⁶ each independently represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and X ^{1 to} X ¹² each independently represents a carbon number. A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted group having 7 to 10 carbon atoms An aralkyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and q ^{1 to} q ¹² each independently represents an integer of 0 or 1) (A) at least a hydrogen atom of the phenolic hydroxyl group of a compound having a phenolic hydroxyl group obtained by condensing a compound represented by the following general formula (3) and a compound represented by the following general formula (4) A curable main agent comprising a compound in which two are substituted with a group having a polymerizable functional group;
(B) The curable composition for laminated boards containing a hardening | curing agent.

(In the general formula (3), X represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, q is 0 or 1 Indicates an integer)

(In the general formula (4), R represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms)   The curable composition for laminated boards according to claim 4, wherein R in the general formula (4) is a propylene group.