JPS62141084A - Thermosetting adhesive - Google Patents

Abstract

PURPOSE:To obtain the titled adhesive which gives a bonded structure having excellent heat resistance, water resistance, and bond strength, by reacting and heat curing either a mixture of a condensed polycyclic aromatic compound, an aromatic crosslinking agent, and an acid catalyst, or a thermosetting reaction intermediate thereof. CONSTITUTION:The titled adhesive is obtained by mixing the following com ponents. A: either a mixture of one or more of naphthalene, anthracene, pyrene, naphthacene, acenaphthylene, perylene, etc. and derivatives consisting principally of a skeleton thereof, or a condensed polycyclic aromatic compound having at least two rings, such as a heavy oil or pitch of, e.g., petroleum base or coal base. B: an aromatic crosslinking agent consisting of one or more aromatic rings having two or more hydroxymethyl groups and/or halomethyl groups. C: an acid catalyst comprising a mixture of one or more compounds selected from AlCl3, BF3, sulfuric acid, phosphoric acid, organic sulfonic acids, carboxylic acids and their derivatives. The molar ratio of B to A is 0.5-4.0, and the amount of component C is 0.5-10wt% based on A+B. If necessary, a thermosetting reaction intermediate obtained by reacting this mixture at 60-300 deg.C is made to react and heat cure.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel adhesive that has excellent heat resistance, water resistance, and adhesive strength.

(Prior Art) Conventionally, the following adhesives made of thermosetting resins are known.

Adhesives: 11 unsaturated polyester adhesives, phenolic resin adhesives, 11 epoxy resin adhesives, polyisocyanate adhesives, bismaleimide adhesives, thermosetting polyamide adhesives, 7 As a technique for chemically bonding stone and adhesive, glass assembly I&
It has been disclosed that chromium aminoacetate and silane coupling agents are effective surface treating agents for adherends.

In addition, when epoxy tree +115 is used as an adhesive for Kanamaru Kyou'' ArJliR and Adhesive J (edited by RL Wood Chemistry Society), the adhesive strength is determined by the hydroxymethyl group present on the surface of the stone material or in the epoxy resin. Depends on the tl surprise,
The mechanism is that the hydroxymethyl group present in both
(It has been disclosed that this is due to comrades' hydrogen bonds.

Furthermore, in "Kanamaruko: Fir Adhesives and Adhesives" (edited by the Chemical Society of Japan), it is stated that when polyisocyanate is used as an adhesive, hydrogen present on the surface of wood and hydroxyl present on the surface of synthetic fibers Methyl group, skin, I, 1. It has been disclosed that the adhesive is strongly bonded to the adhesive through amino groups, etc., urethane, or bonding bond present on the surface of the adhesive.

Also, JP-A-59-166531 and JP-A-60
Publication No. 32821 discloses a heat-resistant adhesive made of imide-modified epoxy. In addition, Tokukai Showa s'y-
23zsq publication discloses a heat-resistant adhesive made of bismaleide.

(Problem to be invented or solved) Among adhesives made of thermosetting resins, unsaturated polyester adhesives, phenolic resin adhesives, epoxy resin adhesives, polyisocyanate adhesives, thermosetting adhesives, etc. Polyamide adhesives and the like have a low heat distortion temperature, and therefore have a problem of poor storage stability as LA adhesives. In particular, thermosetting polyamide adhesives are expensive. ■The technology described in Japanese Patent Publication No. 36-17081 and Japanese Patent Publication No. 37-2979 introduces chemical bonding, or the material to be covered is limited to a glass composition and the adhesive is limited to an epoxy resin. After that, the problem of heat resistance mentioned in 1) was solved.

Furthermore, when an epoxy resin is used as an adhesive, the adhesion is due to hydrogen bonds between hydroN dimethyl groups, and therefore the bonding force is weaker than chemical bonds based on covalent bonds.

Also, regarding polyisocyanate, it is sensitive to moisture and if
There are some drawbacks, such as the nature and inconvenience of handling.

On the other hand, when Bismaleides 1 to 11 are used as adhesives, they either help in heat resistance or have the disadvantage that the adhesive strength is weaker than when epoxy resin is used with J as an adhesive. Ta. Also, ll11 fever is 300℃ normal temperature.
', the blistering time in tank III was in the range of 70 to 80 minutes.

By the way, at the 51st Autumn Annual Meeting of the Unchemical Society of Japan, which was held in Kanazawa on October 4, 1985, the inventors of the present invention discovered that the fused polycyclic aromatization ('l and at least one of a hydroxymethyl group or a heromethyl group];
He has announced a composite material using a thermosetting composition (COPNA resin M1 composition) formed by reacting an aromatic crosslinking agent consisting of η fragrance with an acid catalyst. (Symposium lecture proceedings 1.p unreleased 1g1 is this thermosetting composition (C
OPNA resin composition) was used as a contacting agent (1)) once.

(1st step and action to solve the problem) In other words, the thermosetting adhesive related to Book 5?5.
- a fused polycyclic aromatic compound; an aromatic crosslinking agent consisting of a one- or one- or two-ring aromatic ring having two or more of at least one of a hydroxymethyl group and a halomethyl group; an acid catalyst; A thermosetting composition (COP) formed by reacting
NA resin composition), the adhesive;
The objective is to provide an adhesive with excellent heat resistance, water resistance, and adhesive strength that can be bonded to stone materials that have surface functional groups or have been introduced by chemically bonding them with surface treatment agents or additives. be.

Hereinafter, the fused polycyclic aromatic compound constituting this adhesive, the crosslinking agent,
Explanations about acid catalysts, surface treatment agents, and adherends f! rl
do.

The fused polycyclic aromatics of the present invention include naphthalene, anthracene, phenanthrene pyrene, chrysene, naphthacene,
It is possible to use a mixture of one or two selected from acenaphthene, acenaphthylene, perylene, coronene, and derivatives having these as skeletons, coal-based or petroleum-based heavy oil, tar, peach, etc.

Next, the crosslinking agent of the present invention contains at least two or more groups of hydroxymethyl groups (or halomethyl groups).
-: (Aromatic compound consisting of 6 aromatic rings or more than 1 ring) such as p-xylylene cyclolite, 1.4
-Benzene dimetatool (p-xylylene glycol)
, 9.10-Anthracendi metatools, etc. can be used.

In addition, the acid catalyst of this 9IjI may be a Lewis acid such as aluminum chloride, boron fluoride, or a protonic acid such as sulfuric acid, phosphoric acid, organic sulfonic acid, carboxylic acid, or a derivative thereof. Alternatively, a mixture of two or more types can be used.

+ii Condensed polycyclic aromatic, cross-linking agent, acid catalyst C0PNA
Regarding the mixing ratio for making an adhesive consisting of resin set L&, crosslinking agent/fused polycyclic aromatic = 0°5 to 4.0 (
(molar ratio) range of 0.5 to 10 w for the mixture of crosslinker/fused polycyclic aromatic for acid catalyst addition.
It was experimentally confirmed that t% is within a suitable range.

In addition, a thermosetting intermediate reaction product (substantially thermal) having plasticity obtained by subjecting a C0PNA resin assembly to a thermal reaction (
It was experimentally confirmed that the reaction temperature range for obtaining the B-stage resin composition is 60 to 300°C, which is a suitable range. By subjecting the C0PNA resin composition to a heating reaction as described in 1- below, an it7 B-stage resin Ml composition is obtained.

Next, as for surface treatment agents and additives, an aromatic crosslinking agent consisting of a monocyclic or bicyclic yJ-smog having at least two or more groups of either hydroxymethyl group or halomethyl group, or It is a mixture of the aromatic crosslinking agent and the acid catalyst, and can be melted by heating to a temperature higher than the melting point of the mixture to form a liquid, or can be dissolved in a solvent and used as a solution3. There is no particular restriction on the addition of the treatment agent or additive to the adherend, but it is preferably in the range of 15 wt% to O and O1.

Adherent materials include hydrogen, halogen, metal,
(Carbon, graphite having or having introduced 13 surface groups of one or more types selected from carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, #anhydride structure) , metal, gold-11 oxide, metal carbide, metal silicide, metal rBide, metal nitride, for metals, glass ml & natural and synthetic polymers-1
When these I and I precursors are used, strong contact and γi strength can be obtained. Surface functionality of Zt material), (etc., glass compositions, natural and synthetic products -(-2 carbon Iil
These things that already exist, such as precursors, remain as they are, while other things exist? If the amount of oxidation is less than 1, it may be introduced by wet oxidation using an oxidizing agent, dry oxidation using oxygen, or reduction treatment such as hydrogenation.

The present invention uses a γ1 material having the characteristics described in 11;) and C0P.
Adhesive consisting of NA resin composition and Hydroxyl Chyl J
, (, Aromatic compounds consisting of one or two or more than one aromatic ring having at least one type of heromethyl group, such as p-xylylenecyclolyne), 9
．． By firmly bonding a surface treatment agent containing an aromatic crosslinking agent such as IO-anthracene dimetatool, the adhesive has excellent one-dimensional stability, strength, and water resistance in addition to heat resistance. We have been able to produce a drug.

The bonding mechanism at the interface of the forefoot adherend is thought to be as follows. That is, due to the action of the acid catalyst contained in the surface treatment agent, the additive, or the contact agent made of the COPNAm fat composition, the crosslinking agent of more than bifunctionality in the surface treatment agent or additive is Material surface water, halogen hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether horizontal placement,
Acid anhydride structure and dehydration, dehalogenation, dehalogenation, arsenic, etc. are bonded by anti-14'; - force is C0PN
YJ aromatic tree in the adhesive 11 consisting of A resin composition! \
Yumata, which is thought to react in the same manner as rogen, human xylino, etc., will result in bonding to the adherend and the C0PNA resin composition with a strength of 1/31 of the bond n1,
Since these reactions are irreversible, they proceed even in water, for example. Therefore, the adhesive of the present invention has excellent water resistance.

The adhesive of the present invention can be produced using a method in which the surface of the adherend is treated with a surface treatment agent in advance, and a method in which the surface treatment agent is used as an additive.
A method can be used in which the surface treatment agent or additive is added to an adhesive made of a 0PNA resin composition, and the surface treatment agent or additive is heated to a temperature higher than its melting point to form a liquid, or it is dissolved in a solvent and used as a solution. Can you
Among these, it is preferable to use a method in which the surface of the adherend is previously treated with a surface treatment agent by dissolving it in a solvent and using a solution.

According to the uninvented invention, an adhesive consisting of a C0PNA resin composition is prepared (1) as an unreacted powder mixture (2) at ++f
ff As a powder of B stage resin composition (3) So-called B
The stage resin composition can be used as a liquid by heating and melting, or (4) the so-called B-stage resin composition can be dissolved in a solvent and used as a liquid.

In addition, as for the adhesive force υ;, hot pressing, fixing with a jig, or the method of Neshi 11-Megasa are used.
The temperature range is preferably 100 to 400°C, and it is necessary to set the bonding temperature and time so that the adhesive hardens with heat after softening, and to fix the adherend so that it does not shift during bonding. There is C.

In addition, J87; In order to obtain a strong product, it is necessary to perform ta, 7i' analysis and adherend material in an oxidizing or non-oxidizing atmosphere -Cl at a temperature of 00 to 400°C Heat within a range for a period of 30 minutes to 1-100 hours,
It is advisable to add a post-curing step that is carried out while maintaining the temperature within the above temperature range.

The bonded structure bonded in this manner has excellent adhesive strength, heat resistance, dimensional stability, water resistance, and the like.

(Example) Next, the present invention will be described in more detail with reference to examples.

Example 1 Commercially available glass cloth and pyrene-phenanthrene C0P
After immersing a composite material consisting of an NA resin matrix in a surface treatment agent consisting of an ethanol solution containing 5 wt% p-xylylene glycol and 1 wt% p-toluenesulfonic acid, it was heated in air for 30 minutes. IP film was used as the adherend. As an adhesive, a mixture of pyrene-phenanthrene (molar ratio 7:3) and p-xylylene glycol were used in a molar ratio of 1:1.5 (117!). B Sudeshi tree 1 was prepared by adding 3-vt% p-trienesulfonic acid to the mixture and reacting at 130°C for 40 minutes.
No. 11 was used. The B-stage resin was heated and melted at 140°C, applied to the surface-treated glass-COPNA wood composite material, and then hot-pressed at 180°C. 20 of this
Post-curing treatment was performed at 0°C for 15 hours. For comparison, a temporary epoxy phenolic adhesive was applied to the glass-COPNA81 resin composite material, hot pressed at 1306°C, and then cured at 150°C for 15 hours. Measurement of stone contact strength18 The results are shown in Table 1.

Table 1 Example 2゜+lj failure J maltized 1 element sintered body in air at 600°C 11
+8 treatment for 11i to add functional groups containing acid 7k to the surface.
? After adding f, this was used as an adhesive. As an adhesive,
Softening + ii: Benzene + 4 solution (medium-average molecular weight: i + L 340) of petroleum pitch at 80°C and p-xylylene glycol with a cell ratio of 12, '+' 1 are mixed together, and l w t is added thereto. % of p-toluenesulfonic acid was reacted at 130° C. for 40 minutes.

This B-stage resin was melted at 130°C, applied to the silicon carbide sintered body, fixed with a jig, and hardened by IJ at 150°C. Subsequently, a post-curing treatment was performed at 200° C. for 10 hours. To examine heat resistance [purpose,
This bonded structure was heated in nitrogen at a temperature increase rate of 20°C/min, and the decrease in tonnage fX was measured. As a result, 4
All < East until 50°C: No decrease in fraud was observed.

Example 3 A commercially available graphite material (trade name: T-6 manufactured by IBIDEN Co., Ltd., 1 bending strength: 1000 kg/c rrr') was heat-treated in air at 500°C for 30 minutes to remove oxygen-containing functional groups on the surface. After introducing p-xylylene glycol: 5
wt%, P-toluenesulfonic acid: 150° in air after immersion in a surface treatment agent consisting of a 1 wt% ethanol solution.
It was heat-treated for 30 minutes at C and used as an adherend. As an adhesive, naphthalene and p-xylylene glycol were mixed in a molar ratio of 21.1 l: 1.75, and 1
The mixture with wt% P-)-luenesulfonic acid added to 1
A B-stage resin reacted at 30'C for 40 minutes was used. This B-stage resin was sandwiched between the adherends as a powder, fixed with a jig, heated to 150°C, and the contact surfaces were tightened and cured at 300°C for the contact γ1 structures. ”1
After rlo time, curing treatment was performed. For the purpose of investigating the degree γ1 strength, the strength of the piece was determined to be K11l, but the fracture occurred from the covered part of the material and there was no change.

Example 4 Although the adhesive structure obtained in Example 3 was treated in fluoridated water for 300 hours, no change was observed.

Example 5 The adhesive structure used in Example 3 was subjected to the same post-curing treatment as in Example 3, and for comparison, a cured product of commercially available phenol resin and hismaleimide was used to cure the adhesive structure using heat in a non-oxidizing atmosphere. Heat Φ by balance, 1,1. The decrease was measured. The results are shown in 1st Z.

(Efficacy of the Invention) As described above, the 4i adhesive according to the present invention provides a primary bonded structure with superior adhesive strength, heat resistance, and water resistance compared to conventional adhesives made of thermosetting resins. Obtainable.

Further, the adhesive according to the present invention has a surface including a book, (5, halogen, hydro(sil group, carbonyl group, (, aldehyde 1- group, epoxy structure, U/71~N structure, needle structure, I
g At least one type selected from among the structures of stagnant water.
Any type of adherend can be bonded as long as there is an adherend that can be used. However, there is no limit to the adherend material.

Furthermore, the adhesive related to undeveloped IJI can be used underwater.

Such adhesives can be used in a wide variety of applications such as structural materials, thermal insulation materials, insulation materials, electronic materials, sliding materials, etc.

4.11-sided tube? i-like explanation

Claims (1)

[Scope of Claims] 1) An aromatic compound consisting mainly of a condensed polycyclic aromatic compound having two or more rings and one or more aromatic rings having two or more of at least one of hydroxymethyl group and halomethyl group. An adhesive comprising a thermosetting composition formed by reacting a group crosslinking agent with an acid catalyst. 2) The adhesive according to claim 1, wherein the adhesive is a mixture of the fused polycyclic aromatic compound, the aromatic crosslinking agent, and the acid catalyst, or a thermosetting intermediate reaction product thereof. An adhesive characterized in that at least one selected from the following is thermally cured by reaction. 3) In the adhesive according to claim 1, the fused polycyclic aromatic compound having two or more rings constituting the adhesive comprises:
naphthalene, anthracene, phenanthrene, pyrene,
Must be one or a mixture of two or more selected from chrysene, naphthacene, acenaphthene, acenaphthylene, perylene, coronene, and derivatives having these as main skeletons, or coal-based or petroleum-based heavy oil, tar, or pitch. An adhesive featuring: 4) In the adhesive according to claim 1, the acid catalyst constituting the adhesive is selected from among aluminum chloride, boron fluoride, sulfuric acid, phosphoric acid, organic sulfonic acids, carboxylic acids, and derivatives thereof. An adhesive characterized by being one selected from the group or a mixture of two or more selected types.