JPH11124562A - Adhesive for molded lignocellulose board, and molded lignocellulose board prepared by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive which enables a molded lignocellulose board with an improved releasability to be produced in a short press time without causing the board to adhere to a heating plate in thermal pressing by using a salicylic acid deriv. (salt) as an internal release agent contained in an aq. emulsion used as an adhesive for lignocellulose materials. SOLUTION: The aq. emulsion contains an org. isocyanate compd. (A), a polyether polyol (B), and an internal release agent (C). Ingredient A is, e.g. polymethylene polyphenylene polyisocyanate. Ingredient A has a ratio of N of 0.1-12.0%, a functionality of 2-8, and a content of -(CHCHO)- of 5-70 wt.%. Ingredient C is represented by formula I or II (wherein R1 to R9 are each H or an alkyl; X1 is H, an alkyl, alkoxy, aralkyl, or halogen; X2 and X3 are each H, an alkyl, alkoxy, or halogen; m is 0 or 1; and n is 1 or 2). 1-70 pts.wt. ingredient B is used based on 100 pts.wt. ingredient A, and 1-150 pts.wt. ingredient C is used based on 100 pts.wt. ingredient B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an organic isocyanate-based adhesive used for producing a hot-pressed board made mainly of lignocellulose, and a lignocellulose molded plate obtained by using the same. A molded product using lignocellulose as a main raw material is called a particle board when lignocellulose is wood chip, and in addition to the particle board, a wafer board using a large chip and an elongated chip (strand) are arranged in one direction. Oriented strand board (OSB), wood fiber (fiber)
In the case of insulation board, medium density fiberboard (MD
F), produced as a hardboard, flooring, wall material,
It is used as a door material, a soundproofing material, a heat insulating material, a tatami mat material, a furniture member, and an automobile member.

[0002]

2. Description of the Related Art Conventionally, a particle board, a wafer board, an OSB, and a fiber board such as a hard board, an MDF, and an insulation board, a rice hull board formed by molding rice hulls, and a corian board formed by molding a corian stalk (hereinafter referred to as a board) Urea resin, melamine resin, urea melamine resin, phenol melamine resin, phenol resin, etc. (hereinafter referred to as formalin resin adhesive) are widely used as adhesives or binders for the production of Have been. These resins are inexpensive, have excellent adhesive properties, and have characteristics of curing in a relatively short time. However, the formalin released from the products after hot-press molding of these formalin-based resin adhesives is regarded as an environmental problem, and in order to reduce the amount of released formalin, in actual use, free Formalin catcher agents and the like are used when the amount of formalin is reduced (the formalin molar ratio of the resin adhesive / the molar ratio of phenol, melamine, and urea is reduced) and when the formalin-based resin adhesive is compounded.

On the other hand, as an adhesive which is non-formalin-based and gives excellent board properties, the use of isocyanate-based adhesives for boards has also been proposed (JP-A-57-131538, JP-A-5-131538). 57-147567, U.S. Pat. Nos. 3,557,263, 3,636,199, 38706.
However, when an organic polyisocyanate is used as an adhesive for a lignocellulosic material and hot-pressed, adhesion to a hot plate occurs due to its excellent adhesiveness. Due to this adhesion, the molded product is damaged, the value as a product is significantly lost, and a great deal of labor is required to remove the attached material from the hot platen. In order to solve these problems, studies have been made on additives to the organic polyisocyanate in order to improve the releasability of the hot platen from the metal. For example, alkyl phosphate or pyrophosphate to organic polyisocyanate (Japanese Patent Publication No. 01-018068), sulfonated compound (Japanese Patent Publication No. 03-038309), wax and liquid ester (Japanese Patent Publication No. 02-054390), aliphatic Carboxylic acids (JP-A-58-36430), polysiloxane compounds (JP-A-61-86205), and fatty acid polymers (US Pat. Nos. 4,772,442 and 4,933,232) have been proposed.

Another method has been proposed in which a release agent is directly applied to a hot platen before hot pressing. For example, formation of a release layer using metal soap (Japanese Patent Laid-Open No. 8-340)
26), high boiling polyols (German Patent No. 1653178)
), Use of a polysiloxane film having a functional group (European Patent No. 1359592), and coating with polytetrafluoroethylene (U.S. Pat. No. 4,347,791). Therefore, at the time of manufacture, some board factories use organic polyisocyanate-based adhesives only for the inner layer that does not touch the hot plate, among the several layers that make up the board. The layer is also manufactured by using a conventional formalin-based resin.

As another solution, for example, in the production of a polyurethane resin molded article, a method using an organic polyisocyanate, a polyol, a cross-linking agent, a catalyst, and an internal mold release agent (JP-A-60-245622) is known. Proposed. However, this method is a method of adding a maximum of 5 parts by weight of zinc stearate to 100 parts by weight of a polyol, and is a method for producing a foam and an elastomer obtained by casting into a mold in the first place. Is not a sufficient solution for the purpose of

In addition, as a release composition, a release composition in which a zinc salt of an aliphatic carboxylic acid is dissolved in a polyol (JP-A-63-137933), a metal salt of a higher fatty acid and N,
Release composition comprising N, N'-tris (2-hydroxypropyl) ethylenediamine (JP-A-63-7275)
7) has been proposed. However, the number of parts of the aliphatic carboxylic acid zinc salt or higher fatty acid metal salt used in the polyol is different, the composition of the polyol is completely different, the system used is non-aqueous, and the purpose of use is to produce a polyurethane molded product. This is not a sufficient solution for the purpose of the present invention. In addition, any of these methods has various problems such as low solubility in organic polyisocyanates such as aliphatic carboxylic acid metal salts and waxes, alkyl phosphates, and polysiloxanes, and poor mold release performance. However, it cannot be used in actual manufacturing sites, and at present, there is no technology that satisfies all of the process, economy, and physical properties.

[0007]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is as follows:
A novel organic polyisocyanate-based adhesive that can solve the problems of physical properties and can produce a high-quality board at low cost without adhering to a hot plate in the production of a lignocellulose molded plate,
Another object of the present invention is to provide a lignocellulose molded plate having excellent performance obtained by using this adhesive.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, using a specific salicylic acid derivative or a salt of the derivative as an internal release agent, an organic polyisocyanate compound and A water emulsified liquid emulsified in water with polyether polyol is used as an adhesive for the production of a hot-pressed board made mainly of lignocellulose. No adhesion to the board, good productivity, and found that it is possible to provide a lignocellulose molded plate of excellent performance,
The present invention has been completed.

That is, the present invention provides (1) (A) an organic isocyanate compound, (B) a polyether polyol, and (C) (a) a compound represented by the general formula (1):

Embedded image [In the formula (1), R _{1 to} R ₅ represent a hydrogen atom or an alkyl group, and X ₁ represents a hydrogen atom, an alkyl group, an alkoxy group,
An aralkyl group or a halogen atom, X ₂ and X
₃ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom], (b) a salt of the salicylic acid derivative represented by the general formula (1), (c) a general formula (2)

Embedded image [In the formula (2), R _{6 to} R ₉ represent a hydrogen atom or an alkyl group, and X ₁ represents a hydrogen atom, an alkyl group, an alkoxy group,
Represents an aralkyl group or a halogen atom, m represents 0 or 1, and n represents 1 or 2], and (c) a salt of a salicylic acid derivative represented by the general formula (2). An adhesive for a lignocellulose molded plate containing at least one internal release agent selected from the group.

[0010] Preferably, (2) the polyether polyol (B) has a nitrogen atom ratio of 0.1% in the molecule.
From 1 to 12.0%, a functionality of 2~8, - (CH ₂ CH ₂
O)-is 5 to 70% by weight of a repeating unit, and
The polyether polyol (B) is used in an amount of 1 to 70 parts by weight based on 100 parts by weight of the organic isocyanate compound (A), and the internal release agent (C) is used in an amount of 1 to 150 parts by weight based on 100 parts by weight of the polyether polyol (B). (1) the adhesive for a lignocellulose molded plate according to (1),

(3) The polyether polyol (B) is
Monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, orthotoluenediamine, metatoluenediamine,
An alkylene oxide is added to one or more compounds selected from diphenylmethanediamine and polyphenylpolymethylenepolyamine, and the content of ethylene oxide in the alkylene oxide is 5 to 70% by weight based on the polyether polyol. An adhesive for a lignocellulose molded plate according to the above (1),

(4) When the salt of the salicylic acid derivative represented by the general formula (1) or the salt of the salicylic acid derivative represented by the general formula (2) is zinc, iron, aluminum, calcium, zirconium, magnesium, barium, nickel , An adhesive for a lignocellulose molded plate according to the above (1), which is a metal salt of copper or cobalt;

(5) Organic isocyanate compound (A)
Is a polymethylene polyphenyl polyisocyanate, the adhesive for a lignocellulose molded plate of the above (1), and

(6) A lignocellulose molded plate obtained by mixing a lignocellulose-based material with the lignocellulose-based material of the above (1) as a water-emulsified liquid and then performing hot-pressing. is there.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the adhesive of the present invention, the organic isocyanate-based compound (A) may be any substance having an isocyanate group. For example, tolylene diisocyanate,
4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, polymethylene polyphenyl polyisocyanate (polymeric MDI), or the above isocyanate compound with active hydrogen Modified isocyanates modified with one or more compounds are included. Among them, polymeric MDI is preferred from the viewpoint of economy.

In the adhesive of the present invention, the polyether polyol (B) is a polyether polyol having 2 to 8 functional groups and a hydroxyl value (OHv) of 24 to 800 mgKOH / g, and-(CH ₂ CH ₂ O) The repeating unit of-may be from 5 to 70% by weight in the molecule of the polyether polyol (B). The polyether polyol (B) is
An initiator is a low-molecular compound having two or more active hydrogens, and an ethylene oxide, propylene oxide, butylene oxide, alkylene oxide having an epoxy group in a molecule such as styrene oxide is used without a catalyst or an alkali metal hydroxide, 3
It is produced by adding a known amine as a catalyst by a known method for producing a normal polyol.

The above-mentioned initiators include amine-based initiators such as ethanolamines such as monoethanolamine, diethanolamine and triethanolamine, ethylenediamine, diethylenetriamine, orthotolylenediamine, metatolylenediamine, 4,4'- Diphenylmethanediamine, 2,4′-diphenylmethanediamine,
Examples thereof include amines such as polymethyl polyphenyl polyamine, and these can be used alone or in combination. Also, non-amine initiators, i.e., glycerin, sucrose, pentaerythritol, sorbitol, trimethylolpropane, diglycerin, propylene glycol, dipropylene glycol, diethylene glycol, ethylene glycol, 1,4-butanediol,
It may be used by mixing with alcohols such as 1,2-butanediol and the like, phenols such as hydroquinone, bisphenol A and novolak.

Preferred initiators are the above-mentioned amine-based initiators, and use of these amine-based initiators in combination with non-amine-based initiators does not matter at all. The ratio of nitrogen atoms in the polyether polyol (B) molecule is from 0.1 to
12.0% is preferable, and if it is less than 0.1%, it cannot be efficiently emulsified, and if it is more than 12.0%, the reaction becomes too fast and there is a problem in production, which is not preferable.

In the adhesive of the present invention, the internal release agent (C) comprises (a) a salicylic acid derivative represented by the general formula (1), and (b) a salicylic acid derivative represented by the general formula (1). A salt, (c) at least one selected from the group consisting of a salicylic acid derivative represented by the general formula (2) and a salt of a salicylic acid derivative represented by the general formula (2) as an active ingredient. . That is, the salicylic acid derivative represented by the general formula (1), the salt of the derivative, the salicylic acid derivative represented by the general formula (2), and the salt of the derivative may be used alone or in combination of two or more. May be used in combination. Even when each of them is used alone, it shows excellent internal release properties, but the combined use can further improve the internal release properties. In addition, since each salicylic acid derivative and the metal salt of the derivative used in the present invention can be made into an emulsion having excellent emulsifiability, it can be expected that the effect on internal mold release acts uniformly when added to a resin or the like. .

In the salicylic acid derivative represented by the general formula (1), R _{1 to} R ₅ represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, Ethyl group, n-propyl group,
Isopropyl group, n-butyl group, isobutyl group and se
c-butyl group), and more preferably a hydrogen atom or a methyl group. In the salicylic acid derivative represented by the general formula (1), X ₁ represents a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group or a halogen atom, and is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (for example, Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group), an alkoxy group having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group), an aralkyl group having 7 to 30 carbon atoms ( For example, a benzyl group, 2
-Methylbenzyl group, 4-methylbenzyl group, 4-chlorobenzyl group, phenethyl group, α-methylbenzyl group,
α, α-dimethylbenzyl group, 1,3-diphenylbutyl group), a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), more preferably a hydrogen atom,
An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a fluorine atom and a chlorine atom, particularly preferably a hydrogen atom, a methyl group or an α-methylbenzyl group It is.

In the salicylic acid derivative represented by the general formula (1), X ₂ and X ₃ represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms. (E.g., methyl, ethyl, n-propyl, isopropyl, n-
Butyl group, isobutyl group, tert-butyl group), carbon number 1
To 4 alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group), halogen atom (fluorine atom,
A chlorine atom or a bromine atom), and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the general formula (1), the substitution position of X ₁ is at the 3-, 4-, 5- or 6-position in the salicylic acid skeleton, preferably at the 3- or 5-position. In the general formula (1), the substitution positions of the 1,3-diphenylpropyl derivative group are 3-position, 4-position in the salicylic acid skeleton.
Position 5, 5 or 6 position, preferably position 3 or 5
Rank.

Examples of the salicylic acid derivative represented by the general formula (1) include, for example, 3- (1 ′, 3′-diphenylbutyl) salicylic acid, 3- [1 ′, 3′-di (2 ″ -methylphenyl) Butyl] salicylic acid, 3- [1 ′, 3′-di (3 ″ -methylphenyl) butyl] salicylic acid, 3-
[1 ', 3'-di (4 "-methylphenyl) butyl] salicylic acid, 3- [1', 3'-di (2" -ethylphenyl) butyl] salicylic acid, 3- [1 ', 3'-di (4 "
-Ethylphenyl) butyl] salicylic acid, 3- [1 ′,
3'-di (4 "-isopropylphenyl) butyl] salicylic acid, 3- [1 ', 3'-di (4" -n-butylphenyl) butyl] salicylic acid, 3- [1', 3'-di (4 "-Tert-butylphenyl) butyl] salicylic acid,
3- [1 ′, 3′-di (3 ″ -methoxyphenyl) butyl] salicylic acid, 3- [1 ′, 3′-di (4 ″ -methoxyphenyl) butyl] salicylic acid, 3- [1 ′, 3 ′ −
Di (4 "-ethoxyphenyl) butyl] salicylic acid, 3
-[1 '-(4 "-methylphenyl) -3'-phenylbutyl] salicylic acid, 3- [1'-phenyl-3'-
(4 "-methylphenyl) butyl] salicylic acid, 3-
[1′-phenyl-3 ′-(4 ″ -tert-butylphenyl) butyl] salicylic acid,

3- [1 ', 3'-di (4 "-fluorophenyl) butyl] salicylic acid, 3- [1', 3'-di (2" -chlorophenyl) butyl] salicylic acid,
[1 ′, 3′-di (4 ″ -chlorophenyl) butyl] salicylic acid, 3- [1 ′, 3′-di (4 ″ -bromophenyl) butyl] salicylic acid, 3- (1 ′, 3′-dimethyl-) 1 ', 3'-diphenylbutyl) salicylic acid, 4-methoxy-3- (1', 3'-diphenylbutyl) salicylic acid, 4-ethoxy-3- (1 ', 3'-diphenylbutyl) salicylic acid, 5-methyl -3- (1 ', 3'-diphenylbutyl) salicylic acid, 5-tert-butyl-3-
(1 ′, 3′-diphenylbutyl) salicylic acid, 5-methoxy-3- (1 ′, 3′-diphenylbutyl) salicylic acid, 5-n-butoxy-3- (1 ′, 3′-diphenylbutyl) salicylic acid, 5-fluoro-3- (1 ′,
3'-diphenylbutyl) salicylic acid, 5-chloro-3
-(1 ', 3'-diphenylbutyl) salicylic acid, 5-
Benzyl-3- (1 ′, 3′-diphenylbutyl) salicylic acid, 5- (4′-methylbenzyl) -3- (1 ′,
3′-diphenylbutyl) salicylic acid, 5- (4′-chlorobenzyl) -3- (1 ′, 3′-diphenylbutyl) salicylic acid, 5-α-methylbenzyl-3-
(1 ′, 3′-diphenylbutyl) salicylic acid, 5-
(Α, α-dimethylbenzyl) -3- (1 ′, 3′-diphenylbutyl) salicylic acid, 5- (α, α-dimethylbenzyl) -3- (1 ′, 3′-dimethyl-1 ′, 3 ′
-Diphenylbutyl) salicylic acid, 6-ethyl-3-
(1 ′, 3′-diphenylbutyl) salicylic acid, 4-
(1 ′, 3′-diphenylbutyl) salicylic acid, 4-
[1 ′, 3′-di (4 ″ -methylphenyl) butyl] salicylic acid, 4- [1 ′, 3′-di (4 ″ -chlorophenyl) butyl] salicylic acid,

5- (1 ′, 3′-diphenylbutyl) salicylic acid, 5- [1 ′, 3′-di (2 ″ -methylphenyl) butyl] salicylic acid, 5- [1 ′, 3′-di (4 "
-Methylphenyl) butyl] salicylic acid, 5- [1 ′,
3'-di (4 "-ethylphenyl) butyl] salicylic acid, 5- [1 ', 3'-di (3" -isopropylphenyl) butyl] salicylic acid, 5- [1', 3'-di (4 "
-Sec-butylphenyl) butyl] salicylic acid, 5-
[1 ', 3'-di (4 "-tert-butylphenyl) butyl] salicylic acid, 5- [1', 3'-di (2" -methoxyphenyl) butyl] salicylic acid, 5- [1 ', 3' −
Di (4 "-methoxyphenyl) butyl] salicylic acid, 5
-[1 ', 3'-di (4 "-n-butoxyphenyl) butyl] salicylic acid, 5- [1'-(4" -methylphenyl) -3'-phenylbutyl] salicylic acid, 5- [1 '
-Phenyl-3 '-(4 "-methylphenyl) butyl]
Salicylic acid, 5- [1′-phenyl-3 ′-(4 ″ -te
rt-butylphenyl) butyl] salicylic acid, 5-
[1 ′, 3′-di (4 ″ -fluorophenyl) butyl]
Salicylic acid, 5- [1 ′, 5′-di (3 ″ -chlorophenyl) butyl] salicylic acid, 5- [1 ′, 3′-di (4 ″ -chlorophenyl) butyl] salicylic acid, 5-
(1 ′, 3′-dimethyl-1 ′, 3′-diphenylbutyl) salicylic acid, 3-methyl-5- (1 ′, 3′-diphenylbutyl) salicylic acid, 3-methoxy-5
(1 ′, 3′-diphenylbutyl) salicylic acid, 3-chloro-5- (1 ′, 3′-diphenylbutyl) salicylic acid,

3-benzyl-5- (1 ', 3'-diphenylbutyl) salicylic acid, 3- (2'-methylbenzyl) -5- (1', 3'-diphenylbutyl) salicylic acid, 3- (4 ' -Methylbenzyl) -5- (1 ', 3'
-Diphenylbutyl) salicylic acid, 3- (4'-methoxybenzyl) -5- (1 ', 3'-diphenylbutyl)
Salicylic acid, 3- (2'-chlorobenzyl) -5
(1 ′, 3′-diphenylbutyl) salicylic acid, 3-
(4'-chlorobenzyl) -5- (1 ', 3'-diphenylbutyl) salicylic acid, 3-phenethyl-5-
(1 ′, 3′-diphenylbutyl) salicylic acid, 3-α
-Methylbenzyl-5- (1 ', 3'-diphenylbutyl) salicylic acid, 3- (α, α-dimethylbenzyl)-
5- (1 ′, 3′-diphenylbutyl) salicylic acid, 3
-(Α, α-dimethylbenzyl) -5- (1 ′, 3′-
Dimethyl-1 ′, 3′-diphenylbutyl) salicylic acid, 3,5-di (1 ′, 3′-diphenylbutyl) salicylic acid, 3,5-di [1 ′, 3′-di (4 ″ -methylphenyl) Butyl] salicylic acid, 3,5-di [1 ′, 3 ′
-Di (4 "-ethylphenyl) butyl] salicylic acid,
3,5-di [1 ′, 3′-di (4 ″ -tert-butylphenyl) butyl] salicylic acid, 3,5-di [1 ′, 3′-
Di (4 "-methoxyphenyl) butyl] salicylic acid,
3,5-di [1 ′, 3′-di (2 ″ -fluorophenyl) butyl] salicylic acid, 3,5-di [1 ′, 3′-di (4 ″ -chlorophenyl) butyl] salicylic acid, 4-ethyl -5- (1 ', 3'-diphenylbutyl) salicylic acid, 4-chloro-5- (1', 3'-diphenylbutyl) salicylic acid, 4-fluoro-5- (1 ', 3'-diphenylbutyl) salicylic acid , 4-methoxy-5
Examples thereof include (1 ′, 3′-diphenylbutyl) salicylic acid, 4-ethoxy-5- (1 ′, 3′-diphenylbutyl) salicylic acid, and 6- (1 ′, 3′-diphenylbutyl) salicylic acid. Of course, the present invention is not limited to these. These salicylic acid derivatives may be used alone or in combination.

In the salicylic acid derivative represented by the general formula (2), R _{6 to} R ₉ represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, Ethyl group, n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec-
Butyl), and more preferably a hydrogen atom or a methyl group. In the salicylic acid derivative represented by the general formula (2), the substitution position of the benzyl derivative group is the 3-, 4-, 5- or 6-position in the salicylic acid skeleton;
Preferably, it is the 3rd or 5th position. In the general formula (2), X ₁ is the same as that in the general formula (1).

Examples of the salicylic acid derivative represented by the general formula (2) include, for example, salicylic acid having one benzyl derivative group.
One reacted benzyl derivative group was reacted with the benzyl group of the monosubstituted salicylic acid derivative (m = 0 and n = 1 in the formula (2)) and one benzyl derivative group reacted with salicylic acid. Salicylic acid derivatives (also m = 1 and n = 1), disubstituted salicylic acid derivatives such as salicylic acid derivatives obtained by reacting two benzyl derivative groups with salicylic acid (also m = 0 and n = 2), or benzyl derivatives with salicylic acid Trisubstituted salicylic acid derivatives in which one benzyl derivative group further reacts with the benzyl group of a disubstituted salicylic acid derivative in which two groups have reacted (similarly, m = 2 and n = 1), and the like. Are monosubstituted, disubstituted and 3 substituted
Each of the substituents may be used alone, and furthermore, 1-substituted and 2-substituted, 1-substituted and 3-substituted, 2-substituted and 3-substituted, or 1-substituted, 2-substituted and 3-substituted It can be used as a mixture. The mixing ratio of each substituent in the salicylic acid derivative mixture composed of mono-substituted, di-substituted and tri-substituted is not particularly limited,
The monosubstitute is about 5 to 95% by weight, and the disubstituted and / or trisubstituted is about 95 to 5% by weight, preferably,
The monosubstitute is about 10 to 90% by weight and the disubstituted and / or trisubstituted is about 90 to 10% by weight. Further, the mixing ratio of the di-substituted product and the tri-substituted product is not particularly limited.
Substituents range from 95 to 5% by weight.

Examples of the salicylic acid derivative represented by the general formula (2) include, for example, 3-benzylsalicylic acid, 3-α-
Methylbenzyl salicylic acid, 3- (α, α-dimethylbenzyl) salicylic acid, 3- (α-methyl-α-ethylbenzyl) salicylic acid, 3- (α-methyl-α-propylbenzyl) salicylic acid, 3- (α-methyl -Α-isobutylbenzyl) salicylic acid, 5-benzylsalicylic acid,
5-α-methylbenzylsalicylic acid, 5- (α, α-dimethylbenzyl) salicylic acid, 5- (α-methyl-α-
Ethylbenzyl) salicylic acid, 5- (α-methyl-α-
Propylbenzyl) salicylic acid, 5- (α-methyl-α
Monosubstituted salicylic acid derivatives such as -isobutylbenzyl) salicylic acid, 3,5-dibenzylsalicylic acid, 3,5
-Di (α-methylbenzyl) salicylic acid, 3-benzyl-5-α-methylbenzylsalicylic acid, 3-α-methylbenzyl-5-α, α-dimethylbenzylsalicylic acid,
2-substituted salicylic acid derivatives such as 3- [4 ′-(α-methylbenzyl) -α-methylbenzyl] salicylic acid and 5- [4 ′-(α-methylbenzyl) -α-methylbenzyl] salicylic acid;

3-benzyl-5- [4 '-(α-methylbenzyl) -α-methylbenzyl] salicylic acid, 3-α
-Methylbenzyl-5- [4 '-(α-methylbenzyl) -α-methylbenzyl] salicylic acid, 3- (4'-
Methyl-α-methylbenzyl) -5- [4 ′-(α-methylbenzyl) -α-methylbenzyl] salicylic acid, 3
-Α, α-dimethylbenzyl-5- [4 ′-(α-methylbenzyl) -α-methylbenzyl] salicylic acid, 3-
Trisubstituted salicylic acid derivatives such as [4 ′-(α-methylbenzyl) -α-methylbenzyl] -5-α-methylbenzylsalicylic acid can be mentioned, but of course, the present invention is not limited to these. Absent.

Each salicylic acid derivative according to the present invention can be prepared by a method known per se (for example, JP-B-60-43317, JP-A-2-91042, JP-B-51-251).
No. 74, Japanese Unexamined Patent Application Publication No. 2-91043, Japanese Unexamined Patent Application Publication No.
221125, Japanese Patent Publication No. 5-61110, Japanese Patent Publication No. 5-75735, and the method described in Japanese Patent Publication No. 5-75736.

That is, the salicylic acid derivative represented by the general formula (1) used in the present invention is obtained, for example, by reacting a phenol derivative represented by the general formula (3) with carbon dioxide in the presence of a base (Kolbe-Schmidt reaction). ). Further, for example, it can be produced by reacting a salicylic acid derivative represented by the general formula (4) with a dimer of a styrene derivative represented by the general formula (5) or (6) in the presence of an acid. it can.

[0033]

Embedded image

Embedded image

Embedded image

Embedded image (In the formulas (3) to (6), R _{1 to} R ₅ and X _{1 to} X ₃ represent the same meaning as described above, and R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group.) The dimer of the styrene derivative represented by 5) or the general formula (6) can be prepared by a known method from the styrene derivative [for example, JP-A-51-115449, J. Am. Or
g. Chem. , 18, 1701 (1953); O
rg. Chem. , 19, 17 (1953); Am
er. Chem. Soc. , 74, 4848 (195
2). Amer. Chem. Soc. , 80,17
61 (1958)].

The salicylic acid derivative represented by the general formula (2) used in the present invention is obtained, for example, by reacting a phenol derivative represented by the general formula (7) with carbon dioxide in the presence of a base (Kolbe-Schmidt reaction). ). Further, for example, a salicylic acid derivative represented by the general formula (4) and a benzyl alcohol derivative, a benzyl alkyl ether derivative, a benzyl halide derivative or a styrene derivative represented by the general formula (9) represented by the general formula (8) are used. It can also be produced by reacting in the presence of an acid.

[0035]

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Embedded image (In the formulas (7) to (9), R _{6 to} R ₉ represent the same meaning as described above, R _{12 to} R ₁₄ represent a hydrogen atom or an alkyl group, Y represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms. Or a halogen atom.) In addition, a mixture of the salicylic acid derivative represented by the general formula (1) and the salicylic acid derivative represented by the general formula (2) is, for example, a phenol derivative represented by the general formula (4). Can be produced at once by reacting a styrene derivative represented by the general formula (9).

The salt of each salicylic acid derivative used in the present invention is not particularly limited, and includes all salts capable of interacting with each salicylic acid derivative to form a salt. Salts, ammonium salts or organic salts, more preferably metal salts, and particularly preferably monovalent, divalent, trivalent and tetravalent metal salts. As the salt, for example, sodium, potassium, lithium, zinc, magnesium, calcium, beryllium,
Barium, nickel, tin, copper, molybdenum, tungsten, zirconium, manganese, cobalt, gallium,
Metal salts such as germanium, titanium, aluminum, iron, gold, silver, platinum and palladium; ammonium salts; methylamine, ethylamine, butylamine, dimethylamine,
Diethylamine, trimethylamine, triethylamine, ethanolamine, isopropanolamine, triethanolamine, 2-dimethylaminoethanol, ethylenediamine, morpholine, piperidine, aniline,
Organic salts of organic amines such as N, N-dimethylaniline can be mentioned, and preferred are metal salts of zinc, iron, aluminum, calcium, zirconium, magnesium, barium, nickel, copper or cobalt.

The salt of each salicylic acid derivative according to the present invention is
For example, when the salt is an alkali metal salt, an ammonium salt or an organic salt, an equivalent amount of an alkali metal hydroxide compound, an alkali metal carbonate compound, or an alkali metal hydrogen carbonate compound (e.g., , Sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate), ammonia or an organic amine compound (eg, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine,
By reacting ethanolamine, isopropanolamine, triethanolamine, 2-dimethylaminoethanol, morpholine) in the presence of water, the alkali metal salt, ammonium salt or amine salt of the salicylic acid derivative can be produced.

When the salt of each salicylic acid derivative according to the present invention is, for example, a monovalent to tetravalent metal salt (other than an alkali metal salt), the above-mentioned alkali metal salt or ammonium salt of the salicylic acid derivative may be used. 0.8 to equivalent
The metal salt of the salicylic acid derivative can be produced by reacting 1.5 equivalents, preferably 1.0 to 1.2 equivalents of the corresponding monovalent to tetravalent metal compound in the presence of water. . In this case, for example, in the case of a divalent metal compound (for example, zinc sulfate), 0.5 equivalent of 2 moles per 1 mole of the alkali metal salt or ammonium salt of the salicylic acid derivative is used. Valent metal compound corresponds to one equivalent. At this time, if necessary, heating may be performed, or an organic solvent may coexist.

The above-mentioned monovalent to tetravalent metal compounds include, for example, sulfates such as zinc sulfate, silver sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, etc., for example, zinc chloride, zinc bromide, silver chloride, iodide. Silver, magnesium chloride,
Halides such as calcium chloride, barium chloride, nickel chloride, cobalt chloride and aluminum chloride, for example,
Acetates such as zinc acetate and manganese acetate, for example, nitrates such as zinc nitrate, calcium nitrate, aluminum nitrate, cobalt nitrate, copper nitrate, nickel nitrate, silver nitrate and the like, but are not limited thereto.

The salt of the salicylic acid derivative according to the present invention is
Salts produced using one or more salicylic acids, for example 3
-Α-methylbenzyl-5- (1,3-diphenylbutyl) salicylic acid, 5- (1,3-diphenylbutyl) salicylic acid, 3,5-di (α-methylbenzyl) salicylic acid and 5-α-methylbenzylsalicylic acid A zinc salt prepared by reacting a mixture of the above respective alkali metal salts with zinc sulfate or zinc chloride can also be used as the internal mold release agent. Further, the salt of each salicylic acid derivative according to the present invention produced as described above may sometimes form a solvate such as a hydrate, depending on the production conditions, the type of salicylic acid derivative or the type of salt. However, needless to say, the solvate can also be suitably used as an active ingredient of the internal release agent of the present invention.

In the present invention, the internal release agent (C) is a salicylic acid derivative represented by the above general formula (1), a salt of the derivative, a salicylic acid derivative represented by the above general formula (2), At least one selected from the group consisting of salt
Species is used as an active ingredient, that is, these salicylic acid derivatives and salts of the derivatives may be used alone or in combination of two or more. Examples of the combination of the mixture include a salicylic acid derivative represented by the general formula (1) and a salicylic acid derivative represented by the general formula (2), and a salicylic acid derivative represented by the general formula (1) and a salicylic acid derivative represented by the general formula (2). A salt of the salicylic acid derivative represented by the general formula (1) and a salt of the salicylic acid derivative represented by the general formula (1)
And a combination of a salt of a salicylic acid derivative represented by the general formula (1) and a salt of a salicylic acid derivative represented by the general formula (2). The mixture may be any combination. The effect is also obtained, and a plurality of them may be used in combination.

In the present invention, when a salicylic acid derivative and / or a salt of the derivative as an active ingredient as an internal release agent is used as a mixture, the mixing ratio of the mixture is not particularly limited. Usually, the salicylic acid derivative represented by the general formula (2) and / or the salt 95 of the salicylic acid derivative represented by the general formula (2) are present in an amount of 5 to 95% by weight based on the salicylic acid derivative represented by the general formula (1).
Preferably, it is in the range of 10 to 90% by weight / 90 to 10% by weight.

In the present invention, the mode of use of the internal release agent (C) is not limited as long as the desired effects of the present invention are not impaired.
Although not particularly limited, it may be used in a neat state (liquid or solid state, pellet state), or may be dissolved in various solvents and used in a liquid state. Further, for example, a surfactant or an emulsifier may be used to emulsify in the presence of water or an organic solvent to obtain a dispersed internal release agent. The content of the internal release agent (C) in the adhesive component is not particularly limited, but is usually 0.1% (weight ratio) or more of the solid content of the adhesive, preferably 1%. That is all.

Specific examples of the solvent used in preparing the adhesive of the present invention include, for example, water, and further, for example,
Benzene, toluene, xylene, ethylbenzene, 1-
Hydrocarbon solvents such as methylnaphthalene, hexane, octane, decane, cyclohexane; halogenated hydrocarbon solvents such as dichloromethane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, tetrachloroethylene, chlorobenzene, dichlorobenzene, chlorotoluene; acetone, methyl ethyl ketone; Ketone solvents such as methyl isobutyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, triethylene glycol, propylene glycol, and glycerol; Ester solvents such as ethyl acetate, butyl acetate and amyl acetate; diethyl ether, diisopropane Pill ether, anisole,
Ether solvents such as diphenyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane; N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-
Nitrogen-containing aprotic polar solvents such as methyl-2-pyrrolidone and N, N'-dimethyl-2-imidazolidinone; for example, sulfur-containing aprotic polar solvents such as dimethylsulfoxide, dimethylsulfone and sulfolane; Organic solvents such as aprotic polar solvents, and further, liquid paraffin, spindle oil, light oil, kerosene, machine oil, mineral oils such as lubricating oils, olive oil, rapeseed oil, castor oil, vegetable oils such as soybean oil, and the like. . If necessary, a plurality of these solvents may be used in combination. Of course, for example, water and an organic solvent may be used in combination.

The adhesive of the present invention may further comprise, if necessary, a binder, a surfactant, an ultraviolet absorber, an ultraviolet stabilizer, a filler, a pigment, in addition to the above-mentioned internal release agent (C).
Lubricants (waxes), plasticizers, fragrances, dyes, antioxidants, and the like can be added and blended in any ratio, for example, by a mixing method, a melt mixing method, a dispersion method, or the like.

Examples of the binder include polyvinyl alcohol derivatives such as polyvinyl alcohol, carboxy-modified polyvinyl alcohol, sulfonated-modified polyvinyl alcohol, and alkyl-modified polyvinyl alcohol; methylcellulose, carboxymethylcellulose, and the like.
Cellulose derivatives such as hydroxyethylcellulose and hydroxypropylcellulose; epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic acid copolymer, isobutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylamide, methylol-modified Polyacrylamide, starch, starch derivatives (eg, oxidized starch, etherified starch); casein, gelatin, gum arabic; water-soluble, such as styrene-butadiene rubber latex, acrylonitrile-butadiene latex, methyl acrylate-butadiene latex, and vinyl acetate emulsion And a water-insoluble binder.

Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylphenol ether, sorbitan fatty acid ester, polyoxyethylene polyoxyethylene polyoxypropylene alkyl ether, and alkylolamide. Nonionic surfactant, salt of alkyl sulfate, salt of alkyl sulfonic acid, salt of alkyl aryl sulfonate, salt of dialkyl sulfosuccinic acid, salt of polyoxyethylene alkyl aryl ether phosphate, formalin condensation of naphthalene sulfonic acid Product anionic surfactants.

Examples of the ultraviolet absorber include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives, cyanoacrylate derivatives, and salicylic acid derivatives. Examples of the ultraviolet stabilizer include hindered amine derivatives. Examples of pigments and fillers include, for example, calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, aluminum oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, talc, wax, kaolin, clay, Diatomaceous earth, silica, inorganic pigments such as carbon black, inorganic fillers, such as styrene microballs, nylon particles, urea-formalin fillers, polyethylene particles, cellulose fillers, organic pigments such as starch particles, organic fillers, and the like. Can be

Examples of the lubricant (wax) include paraffin wax, microcrystalline wax, carboxy-modified paraffin wax, carnauba wax,
Examples include polyethylene wax, polystyrene wax, canderia wax, montan wax, higher fatty acid esters, and silicone oil. As a plasticizer,
Examples include ester plasticizers such as dioctyl phthalate, butyl benzyl phthalate, tributyl phthalate, dioctyl adipate, dibutyl sebacate, and acetyl tributyl citrate, polyester plasticizers, and epoxy plasticizers.

The adhesive of the present invention may further contain other internal components such as a wax-based internal release agent, an aliphatic carboxylic acid metal-based internal release agent, so-called metal soap, as long as the desired effects of the present invention are not impaired. It is also possible to use a drug having a releasing effect in combination. In this case, the ratio of the internal release agent (C) according to the present invention to the total internal release agent is not particularly limited, but is usually 20% by weight or more, preferably 40% by weight.
The content is more preferably 50% by weight or more.

The salicylic acid derivative salt may be used as an emulsified product by using an emulsifier, if necessary. The emulsifier in this case may be any commonly used emulsifier, such as fatty acid soap, rosin acid soap, alkyl sulfonate, alkylbenzene sulfonate, dialkylaryl sulfonate, alkyl sulfosuccinate, polyoxyethylene. Alkyl sulfates, anionic surfactants such as polyoxyethylene alkylaryl sulfonates,
Polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan fatty acid ester, surfactants such as oxyethylene oxypropylene block copolymers, but the present invention is not limited to these surfactants Absent. These surfactants may be used alone or in combination of two or more.

In the adhesive of the present invention, the mixing ratio of the organic isocyanate compound (A) and the polyether polyol (B) is determined in accordance with the ratio of the organic isocyanate compound (A).
Has an active hydrogen equivalent of 0.1 with respect to 1 isocyanate group equivalent.
02 to 1.2 are preferred. If it is less than 0.02, the organic isocyanate compound (A) will not disperse in water,
When the ratio is more than 1, the ratio of the isocyanate group reacting with lignocellulose and water decreases, and the physical properties of the board deteriorate, which is not preferable.

In the preparation of the aqueous emulsion of the adhesive of the present invention, the method of emulsifying the organic isocyanate compound (A) in water and the method of mixing the internal release agent (C) are not particularly limited. A method of simultaneously mixing and emulsifying four kinds of the naat-based compound (A) and the polyether polyol (B), the internal release agent (C) and water at a high speed, and dispersing the internal release agent (C) in water in advance. Adding and dissolving a polyether polyol (B), and mixing and emulsifying the organic isocyanate-based compound (A) at a high speed; mixing the polyether polyol (B) with the internal release agent (C) followed by mixing with water A method in which the organic isocyanate compound (A) is added while stirring at a high speed to emulsify the mixture. After mixing the organic isocyanate compound (A) with the internal release agent (C), water and the polyether polyol (B) are mixed. )of A method of mixing and emulsifying in a liquid mixture, a method of mixing a polyether polyol (B), an organic isocyanate-based compound (A), and an internal release agent (C), and then adding the resulting mixture to water with high-speed stirring to emulsify. Or any other method, and various methods can be applied. In each step, a surfactant and a stabilizer may be used as long as the present invention is not inhibited. The mixing system may be a batch system or a continuous system, and a homogenizer, a static mixer or the like can be used. The water content of the aqueous emulsion of the adhesive is not particularly limited, and may be an amount that enables the adhesive to be uniformly mixed with the lignocellulose-based material when the aqueous emulsion is applied to the stability or production of a lignocellulose molded plate. good. Usually, 1 to 200% by weight of the amount of the adhesive is preferable.

In the adhesive of the present invention, the mixing ratio between the organic isocyanate compound (A) and the polyether polyol (B) is (A) :( B) = 100: 1 to 7 by weight.
It is in the range of 0, preferably in the range of 5 to 50. If the polyether polyol (B) is less than 1, a stable water emulsion will not be obtained, and if it exceeds 70, the physical properties of the board will deteriorate.

In the adhesive of the present invention, the mixing ratio of the polyether polyol (B) and the internal release agent (C) is 100 parts by weight of the polyether polyol (B) and the internal release agent (C). 1 to 150 parts by weight is preferred. This is not preferable because the internal mold release agent (C) is less than 1 part by weight, the mold release effect is not exhibited, and the internal mold release agent (C) may adhere to the hot platen during hot pressing. The use of more than 150 parts by weight is industrially useless because the property is obtained.

A lignocellulose molded plate is manufactured using the adhesive of the present invention containing the above-mentioned internal release agent (C).
As lignocellulosic materials, particle board,
Wafer board, strand chip, dust chip, flake chip used for OSB, hard board,
MDF, fibers used for insulation boards and agricultural products such as kollan stalks, pagasu, and rice husks. These raw materials may be used alone or 2
A combination of more than one species can also be used. An adhesive, which is a water emulsion containing the organic polyisocyanate compound (A), the polyether polyol (B) and the internal release agent (C) of the present invention, is mixed with a lignocellulose material. As the method, spraying the aqueous emulsion prepared in advance by the method for preparing the aqueous emulsion onto the lignocellulosic material in the blender, or uniformly mixing the aqueous emulsion and the lignocellulose material Good. The lignocellulosic material may be mixed in the blender at the same time as the preparation of the aqueous emulsion by the above method. At this time, if necessary, the solution may be diluted with a solvent or water to form a solution. However, it is preferable to use an aqueous solution from the viewpoint of economy and safety.

The amount of the adhesive used is determined by the total amount of the organic isocyanate-based compound (A) and the polyether polyol (B), which are active ingredients as an adhesive in the aqueous emulsion of the adhesive: lignocellulose-based material Is 2:10 by weight.
It is in the range of 0 to 30: 100, preferably 3: 100.
20: 100. If it is less than 2, the effect as an adhesive cannot be obtained, and sufficient board properties can be obtained in the range up to 30, so that even if the amount of the adhesive exceeds 30, it is industrially useless. A required amount of the adhesive aqueous emulsion is mixed with a lignocellulose-based material so as to be in the above range to produce a lignocellulose molded plate.

In the lignocellulose molded plate of the present invention, a mixture of the above adhesive and the lignocellulose-based material is formed into a desired shape and hot-pressed. At the time of forming, forming from a single layer to a plurality of layers is possible. If necessary, the content of the adhesive may be changed. Also,
If necessary, pre-pressing may be performed after lamination, or a pre-pressed mat may be laminated before lamination. Further, at this time, the adhesive of the method of the present invention may be used only on the surface layer which comes into contact with the hot plate, and the inner layer may have a multilayer structure using an adhesive having a poor releasability.

The hot press may be a flat press or a curved press in both upper and lower shapes, since the heat only needs to pass through the molding material, but a flat press is preferable in terms of continuous productivity and cost. Further, the press may be a continuous press or a multi-stage press. The outermost layer of the board after hot pressing may be finished by polishing the surface to a desired thickness, if necessary. In the present invention, an antioxidant, an ultraviolet absorber, a plasticizer, a silane coupling agent, poval, a metal catalyst, an external mold release agent, a synthetic rubber latex, and an acrylic emulsion are used in combination within a range not to impair the desired effect. You may. The lignocellulose molded plate of the present invention is characterized in that, due to the excellent releasing effect of the internal release agent (C), not only does the molded plate not adhere to the coal plate during hot pressing, but also the internal release agent The board of the product containing (C) has excellent mechanical properties as well as antibacterial and antifungal effects.

[0060]

Next, the present invention will be described in more detail with reference to examples, but these examples do not limit the present invention in any way. Table 3 shows the evaluation results in Examples and Comparative Examples.
Shown in In the examples, all parts and ratios are by weight unless otherwise specified. The common manufacturing conditions of the boards in the performance comparison are described below. Raw material: dust chips or wood fiber (water content 7.
0%, hereinafter referred to as chip) Board composition: Single layer (dust chip) or 3 layers (wood fiber) Board thickness (excluding polished part): 15mm Mat water content: 16% Hot pressing temperature: 180 ° C Pressing pressure: 35kg / cm ² press time: 2 minutes 30 seconds Set density: 700 kg / m ³

Evaluation Test Flexural strength From the molded sample "Particle board JIS-A-5
508 "width 50 mm, length 27
The test piece was cut to 5 mm (span 225 mm), and a bending strength test was performed. The results were expressed as flexural strength. 2. Flexural strength when wet (A test) The test piece was cut in the same manner as described above. Next, the test piece was immersed in warm water of 70 ± 3 ° C. for 2 hours, immersed in normal temperature water for 1 hour, and then subjected to a bending strength test in a wet state. The results were expressed as wet flexural strength. 3. Releasability Test At the time of hot pressing, a steel-made coal board was used, and the state of attachment of the chip to the cold board after hot pressing was visually confirmed. : No adhesion was observed even after repeating this operation 30 times. 4. Comprehensive judgment The board molding and the physical properties of the board were comprehensively judged. The evaluation symbols indicating the determination results are as follows. ：: The board can be manufactured without any problem, and the physical properties are good. ×: The board cannot be manufactured.

Production Example 1 19.8 g of 2-α-methylbenzylphenol and sulfuric acid 1
g of the mixture was heated to 80 ° C., and 23 g of 1,3-diphenyl-1-butene was added dropwise at the same temperature to carry out a reaction.
After completion of the reaction, toluene was added to the reaction solution, and then the organic layer was washed with water, an aqueous solution of sodium hydrogen carbonate, and an aqueous solution of sodium hydroxide, and the aqueous layer was removed. An aqueous solution of sodium hydroxide was added dropwise to the organic layer under azeotropic dehydration to obtain a toluene solution containing sodium phenoxide. This solution was charged into an autoclave, and carbon dioxide gas was blown at 130 ° C. and 10 atm.
The reaction was performed for 5 hours. After the completion of the reaction, the mixture was cooled to 55 ° C.
The aqueous layer was separated by adding 00 g, and the aqueous layer was further washed with toluene to remove unreacted phenol. The aqueous layer was acidified with diluted hydrochloric acid, and ether was added thereto to extract an organic substance. Then, the ether was distilled off and 3-α-methylbenzyl-5- (1 ′, 3 ′) was extracted.
(Diphenylbutyl) salicylic acid 41 g was obtained. 22.5 g of the obtained 3-α-methylbenzyl-5- (1 ′, 3′-diphenylbutyl) salicylic acid was dissolved at 25 ° C. in an aqueous solution (340 ml) containing 2 g of sodium hydroxide. An aqueous solution (50 ml) containing 7.3 g of zinc sulfate heptahydrate was added dropwise to the aqueous solution at 25 ° C. over 30 minutes while stirring. Further, after stirring at 25 ° C for 30 minutes, the precipitate was filtered, washed with water, and then dried in vacuo at 40 to 50 ° C to give 3-α-methylbenzyl-5- (1 ′, 3′-
23 g of the zinc salt of diphenylbutyl) salicylic acid were prepared.

Production Example 2 41.6 g of styrene was added dropwise to a mixture of 30.4 g of methyl salicylate and 8 g of methanesulfonic acid at 30 to 40 ° C., and reacted at the same temperature for 4 hours. After completion of the reaction, toluene was added to the reaction solution, and then water, an aqueous solution of sodium hydrogen carbonate,
The organic layer was washed with an aqueous sodium hydroxide solution, and the aqueous layer was removed. Then, the solvent was distilled off from the organic layer, and then 50.2 g of 3,5-di (α-methylbenzyl) salicylic acid methyl ester was obtained by distillation under reduced pressure. The obtained 3,5-di (α-methylbenzyl) salicylic acid methyl ester 50
After charging 300 g of water and heating to 98 to 100 ° C., 14 g of a 40% aqueous sodium hydroxide solution was added dropwise over 2 hours, and after completion of the addition, the mixture was reacted for 2 hours to perform hydrolysis. Next, after adding toluene to the reaction solution, neutralizing with dilute sulfuric acid, heating and dissolving to remove the aqueous layer, the solvent was distilled off from the organic layer, and 3,5-di (α-methylbenzyl) salicylic acid was removed. 46 g were obtained. Thereafter, according to the method described in Production Example 1, a zinc salt of 3,5-di (α-methylbenzyl) salicylic acid was produced.

Production Example 3 20 g of a mixture of 3-α-methylbenzyl-5- (1 ′, 3′-diphenylbutyl) salicylic acid and 3,5-di (α-methylbenzyl) salicylic acid (5: 5 molar ratio) was prepared. 2g
25% aqueous solution containing sodium hydroxide (340 ml)
Dissolved at ° C. An aqueous solution (50 ml) containing 7.3 g of zinc sulfate heptahydrate was added dropwise to the aqueous solution at 25 ° C. over 30 minutes while stirring. Further, after stirring at 25 ° C. for 30 minutes, the precipitate was filtered, washed with water, and dried in vacuo at 40 to 50 ° C. to give 3-α-methylbenzyl-5-colorless powder.
(1 ′, 3′-diphenylbutyl) salicylic acid and 3,5
20.7 g of the zinc salt of a mixture of -di (α-methylbenzyl) salicylic acid were prepared.

Production Example 4 20.7 g of salicylic acid, 10 g of acetic acid and 5 g of methanesulfonic acid were added and heated. The internal temperature was adjusted to 110 ° C., and then 62.4 g of styrene was added dropwise at this temperature. After dropping,
After further reacting for 1 hour, the mixture was cooled, 100 ml of heptane was added to the reaction solution, and the organic layer was washed several times with 100 ml of water. After washing with water, 200 ml of an aqueous sodium hydroxide solution was added, and the organic layer was separated and removed. After adding 100 ml of heptane to the aqueous layer and acidifying the aqueous layer with hydrochloric acid, the organic layer was separated and concentrated. The residual oil was further dried under vacuum,
3-α-methylbenzyl-5- (1 ′, 3′-diphenylbutyl) salicylic acid and 5-α-methylbenzyl-3-
(1 ′, 3′-diphenylbutyl) salicylic acid and 3,5-di (α-methylbenzyl) salicylic acid (1:
80.6 g of a mixed salicylic acid (1: 8 molar ratio) was obtained. Using the obtained mixed salicylic acid, according to the method described in Production Example 1, 3-α-methylbenzyl-5- (1 ′, 3 ′)
A zinc salt of a mixture of -diphenylbutyl) salicylic acid and 5-α-methylbenzyl-3- (1 ′, 3′-diphenylbutyl) salicylic acid and 3,5-di (α-methylbenzyl) salicylic acid was prepared.

Production Example 5 1 ′, 3′-Diphenyl-1 was added to a mixture of 15.2 g of methyl salicylate and 4 g of methanesulfonic acid at 30 to 40 ° C.
-20.8 g of butene was added dropwise. After the completion of the dropping, the reaction was further performed at the same temperature for 4 hours. After completion of the reaction, toluene was added to the reaction solution, and then the organic layer was washed with water, an aqueous solution of sodium hydrogen carbonate, and an aqueous solution of sodium hydroxide, and the aqueous layer was removed.
Thereafter, the solvent was distilled off from the organic layer, 70 g of water was charged, and the mixture was heated to 98 to 100 ° C., and 10 g of a 40% aqueous sodium hydroxide solution was added dropwise over 1 hour. The reaction was carried out for hydrolysis. Next, after adding toluene to the reaction solution, neutralizing with dilute sulfuric acid, heating and dissolving to remove the aqueous layer, the solvent was distilled off from the organic layer to obtain a solution.
A crude product of-(1 ', 3'-diphenylbutyl) salicylic acid was obtained. Thereafter, the crude product was purified by recrystallization using a mixed solvent of toluene and n-hexane to obtain 5- (1 ′, 3 ′).
24 g of a purified product of (-diphenylbutyl) salicylic acid was obtained. Then, the obtained 5- (1 ′, 3′-diphenylbutyl) salicylic acid and 3,5-di (α-methylbenzyl)
Salicylic acid was mixed (5: 5 molar ratio). 17.3 g of the mixed salicylic acid was dissolved at 25 ° C. in an aqueous solution (240 ml) containing 2 g of sodium hydroxide. A 1N aqueous silver nitrate solution (50 ml) was added dropwise to the aqueous solution at 25 ° C. over 30 minutes with stirring. Further, for 30 minutes, 25 ° C
After stirring at, the precipitate was filtered, washed with water, and dried. Further, after dissolving the silver salt in 200 ml of acetone at 25 ° C.,
The insoluble material was separated by filtration, acetone was distilled off from the filtrate, and 5-
(1 ′, 3′-diphenylbutyl) salicylic acid, 3,5
A mixture of -di (α-methylbenzyl) salicylic acid (5:
20.7 g of a silver salt (5 mol ratio) was produced. Silver content is 2
It was 3.6% by weight.

Examples 1 to 6 An aqueous emulsion of an adhesive was prepared using the internal release agent obtained in Production Examples. Ethylenediamine (EDA), orthotoluenediamine (OTD), triethanolamine (TEO)
A) Using the mixture as an initiator, 14.8 parts by weight of propylene oxide / ethylene oxide block copolymerized PPG (ethylene oxide content: 40%; hydroxyl value: 252 mg KOH / g) was used as 117 parts.
Part of water, and furthermore polymeric MDI (manufactured by Mitsui Toatsu Chemicals, Inc .; trade name Cosmonate M-200) 5
9.2 parts were charged and emulsified while stirring at a high speed. After emulsification,
3-α-methylbenzyl-5- as an internal release agent
(1 ′, 3′-diphenylbutyl) salicylic acid and 3,5
4.3 parts of a water emulsion (solid content: 35%) of a mixture of -di (α-methylbenzyl) salicylic acid in a 5: 5 molar ratio was added and stirred to obtain a water emulsion. Similarly, aqueous emulsions of adhesives were prepared using aqueous emulsions (solid content: 35%) of various salicylic acid derivatives and salts of the salicylic acid derivatives shown in Table 1. In each case, the aqueous emulsion was very good in stability and emulsification.

Comparative Examples 1 and 2 An aqueous emulsion of an adhesive was prepared in the same manner as in Example 1 except that salicylic acid was used as a sample. Further, an aqueous emulsion of the adhesive containing no salicylic acid was prepared.

Examples 6 to 12 Production of Lignocellulose Molded Board The aqueous emulsion prepared in Example 1 was spray-coated with 820 parts of wood fiber in a blender using a spray gun. Next, a dust chip coated with the water emulsion was uniformly formed on a steel coal plate to a size of 30 cm square, covered with a steel coal plate, and hot-pressed under the above conditions to obtain a molded plate. Was. The time required from the start of emulsification to the start of hot pressing was 20 minutes. After hot pressing, adhesion to the steel coal board was observed, but no adhesion was observed. The board after the hot pressing was used for physical property comparison, and the above operation was repeated using the same coal board again, but no adhesion to the steel coal board was observed even after repeating 50 times. Similarly, a molded plate was similarly obtained using the aqueous emulsion prepared in Examples 2 to 6. In each case, the time required from the start of the emulsification to the start of the hot pressing was approximately 20 minutes, and no adhesion to the steel cold plate was observed after the hot pressing. The molding was repeated by the same operation using the same coal plate, but no adhesion to the steel coal plate was observed even after 50 times. Table 2 shows various physical properties of the obtained lignocellulose molded plate.

Comparative Examples 3 and 4 Example 6 using the aqueous emulsion of the adhesive prepared in Comparative Examples 1 and 2
A press plate was formed in the same manner as described above. However, after hot pressing, adhesion to the steel coal board was observed. If the board was forcibly peeled off, the board surface became uneven, and physical properties could not be measured.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

As is apparent from the above description, the salicylic acid derivative and / or salt thereof of the present invention can be used alone or in combination.
Organic isocyanate-based adhesive containing more than one kind as an internal release agent, when used as an adhesive for lignocellulose-based materials, shortens press time and shows excellent release properties,
A lignocellulose molded plate of good quality can be manufactured with high productivity, and it has excellent mechanical properties and further excellent antibacterial and antifungal properties as a lignocellulose molded plate.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Taku Nago 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside (72) Inventor Ryoman Tanabe 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemical Co., Ltd.

Claims (6)

[Claims] 1. An organic isocyanate compound (A), a polyether polyol (B) and (C) (a) a general formula (1) [In the formula (1), R _{1 to} R ₅ represent a hydrogen atom or an alkyl group, and X ₁ represents a hydrogen atom, an alkyl group, an alkoxy group,
An aralkyl group or a halogen atom, X ₂ and X
₃ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom], (b) a salt of a salicylic acid derivative represented by the general formula (1), (c) a general formula (2) 2] [In the formula (2), R _{6 to} R ₉ represent a hydrogen atom or an alkyl group, and X ₁ represents a hydrogen atom, an alkyl group, an alkoxy group,
Represents an aralkyl group or a halogen atom, m represents 0 or 1, and n represents 1 or 2], and (c) a salt of a salicylic acid derivative represented by the general formula (2). An adhesive for a lignocellulose molded plate containing at least one internal release agent selected from the group. 2. The polyether polyol (B) has a nitrogen atom ratio in the molecule of 0.1 to 12.0% of the whole,
Functionality of _{2~8, - (CH 2 CH 2} O) - and repeating units of 5 to 70 wt%, and 100 parts by weight of polyether polyol of organic isocyanate compound (A) (B) Is 1 to 70 parts by weight, and 100 parts by weight of the polyether polyol (B) is 1 part of the internal release agent (C).
The adhesive for a lignocellulose molded plate according to claim 1, wherein the amount is from 150 to 150 parts by weight. 3. The polyether polyol (B) is monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine,
Ortho-toluenediamine, meta-toluenediamine, diphenylmethanediamine and polyphenylpolymethylene polyamine, at least one compound selected from the group consisting of an alkylene oxide and an alkylene oxide. The adhesive for a lignocellulose molded plate according to claim 1, which is 70% by weight. 4. The method according to claim 1, wherein the salt of the salicylic acid derivative represented by the general formula (1) or the salt of the salicylic acid derivative represented by the general formula (2) is zinc, iron, aluminum, calcium, zirconium, magnesium, barium, nickel, 2. The adhesive for a lignocellulose molded plate according to claim 1, which is a metal salt of copper or cobalt. 5. An organic isocyanate compound (A) comprising:
2. The adhesive for a lignocellulose molded plate according to claim 1, wherein the adhesive is polymethylene polyphenyl polyisocyanate. 6. A lignocellulose molded plate obtained by molding a mixture obtained by mixing the lignocellulose molded plate adhesive according to claim 1 with a lignocellulose-based material as a water emulsion, followed by hot-pressing.