JP3519135B2 - Bonding method of porous material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for adhering a porous material.

[0002]

2. Description of the Related Art Plastic foam, wood, paper, cloth,
As a method of adhering a porous material such as felt and slate, a method of mixing a water-soluble urethane prepolymer and water in the air and using it (for example, Japanese Patent Publication No. 2-34994) is known.

[0003]

However, the conventional method of mixing the water-soluble urethane prepolymer with water in the air is used by diluting it with an organic solvent such as methylene chloride because the prepolymer has a high viscosity. However, there were problems in terms of safety and health and environmental pollution.

[0004]

Means for Solving the Problems The present inventors have proposed a solventless type, a rapid curing type, a low viscosity and an inexpensive collision mixing type sprayer, which can be applied to obtain a low elastic modulus and a high strength adhesive force. The present invention has been achieved as a result of extensive studies on the bonding method for applying. That is, in the present invention, when adhering adherends of which at least one is porous, the following main agent and curing agent main agent: an organic polyisocyanate compound (a) and an oxyethylene chain are formed on at least one surface of the adherends. A mixture of a urethane prepolymer (A) derived from a polyalkylene ether polyol (b1) having a content of 20 to 100% by weight and a water-soluble diluent (B). Hardener: A mixture of water, a water-soluble polyalkylene ether polyol (b2) and, if necessary, a catalyst (C). The method for adhering a porous material is characterized in that the two-component curable solventless adhesive consisting of is applied, and then the two are superposed and pressure-adhered.

Organic polyisocyanate compound (a) constituting the urethane prepolymer (A) in the present invention
For example, (a) an aliphatic polyisocyanate having 2 to 12 carbon atoms [excluding the carbons in the NCO group, and the same applies to (ii) to (ii)]; and (ii) having 4 to 15 carbon atoms. Alicyclic polyisocyanate, (c) aromatic aliphatic polyisocyanate having 8 to 12 carbon atoms, (d) aromatic polyisocyanate having 6 to 30 carbon atoms, (e) modified products of these polyisocyanates, and mixtures thereof. Can be mentioned.

Specific examples of the aliphatic polyisocyanate (a) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
Examples thereof include lysine diisocyanate and 1,3,6-hexamethylene triisocyanate.

Specific examples of the alicyclic polyisocyanate (b) include isophorone diisocyanate (IPDI),
Dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), 1,4-cyclohexane diisocyanate, methylcyclohexane-2,4-diisocyanate (hydrogenated TDI), 1,4-bis (2-isocyanatoethyl) cyclohexane, etc. Can be mentioned.

Specific examples of the araliphatic polyisocyanate (c) include p-xylene diisocyanate and tetramethyl xylene diisocyanate.

Specific examples of the aromatic polyisocyanate (d) include 1,4-phenylene diisocyanate, 2,
4- or 2,6-toluene diisocyanate (TD
I), diphenylmethane-2,4'- or 4,4'-
Diisocyanate (MDI), naphthalene-1,5-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, o-tolidine diisocyanate, crude TDI, polyphenylmethane polyisocyanate (crude MDI) and the like can be mentioned.

Specific examples of the modified polyisocyanate (e) include carbodiimide groups described in (a) to (d) above,
Examples thereof include modified products (carbodiimide-modified MDI, etc.) into which a uretdione group, a uretoimine group, a urea group, a buret group, an isocyanurate group, a urethane group and the like are introduced. Preferred among (a) to (e) are (b) and
(C), (d) and (e).

As the polyalkylene ether polyol (b1) having a content of oxyethylene chains constituting the urethane prepolymer (A) of 20 to 100% by weight, active hydrogen-containing compounds [polyhydric alcohols {aliphatic dihydric alcohols (Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-
Butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octamethylenediol, etc.), low molecular weight diols having a cyclic group [1,4-bis (hydroxymethyl) cyclohexane, m- and p-
Xylylene glycol, 1,4-bis (2-hydroxyethoxy) benzene, 1,4-bis (α-hydroxyisopropyl) benzene, 2,2-bis (4-hydroxyethoxyphenyl) propane, etc.] trihydric alcohol (Glycerin, trimethylolpropane, hexanetriol, etc.), tetrafunctional or higher polyhydric alcohols (sorbitol, sucrose, etc.)}, phenols (hydroquinone, bisphenol A, etc.)], and alkylene oxides (having 2 to 2 carbon atoms). 4 alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide) having 20 to 20 oxyethylene chains.
Examples thereof include those added so as to be 100% by weight (either block addition or random addition).

The active hydrogen equivalent of the polyol (b1) is usually 200 to 10,000, preferably 400 to 5,000.
It is 0. The number of functional groups is usually 2 to 8, preferably 2 to 3.
Is.

The amount of oxyethylene chains in the polyol (b1) is usually 20 to 100% by weight, preferably 40 to 100% by weight, based on the whole (b1). When the amount of the oxyethylene chain is less than 20% by weight, the compatibility with the curing agent becomes poor, resulting in poor curing and insufficient adhesive strength.

The NCO group content of the urethane prepolymer (A) is usually 2 to 15% by weight, preferably 4 to 10% by weight.
Is. If the NCO group content is less than 2% by weight, the adhesive strength becomes insufficient, and if it exceeds 15% by weight, the elastic modulus becomes high and the flexibility is poor.

The water-soluble diluent (B) is not limited as long as it is a water-soluble compound containing no active hydrogen. For example, an average molecular weight of 100 represented by the following general formula (1) or (2) is used. ~ 5000 compounds. ^{X [O- (R 1 O)} n-R 2] m (1) X [O- (R 1 O) n-OC-R 2] m (2) [ wherein, X is an alcohol, a polyhydric alcohol, Alkanolamine, a group excluding OH groups of phenol and bisphenol A, R ¹ is an alkylene group having 2 to 4 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms or a phenyl group (halogen or 1 to 18 carbon atoms). It may be substituted with an alkyl group), n is an integer of 1 to 40, and m is an integer of 1 to 8. Specific examples of the compound represented by the general formula (1) or _{(2), CH 3 O (CH 2 CH} 2 O) 10 CH 3 CH 3 COO (CH 2 CH 2 O) 10 OCCH 3 CH 3 _{O (CH 2 CHCH 3 O)} 5 CH 3 CH 3 CH 2 CH 2 CH 2 O (CH 2 CH 2 O) 10 CH 3 CH 3 CH 2 CH 2 CH 2 O (CH 2 CH 2 O) 10 OCCH 3 etc. Is mentioned. You may use these in mixture of 2 or more types.

In the present invention, the water-soluble diluent (B) is usually used as a mixture with the main agent, and has an action of instantly compatibilizing the main agent and the curing agent. Due to the action, it is possible to perform coating using an impingement mixing type spray machine such as air mixing, and it is possible to prevent problems such as adhesion failure due to poor mixing. The amount of (B) in the main agent is usually 3 to 70.
% By weight. If the amount of (B) is less than 3%, the compatibility with the curing agent will be poor, resulting in poor curing and insufficient adhesive strength, and if it exceeds 70% by weight, the adhesive strength will be poor.

As the water-soluble polyalkylene ether polyol (b2) constituting the curing agent, the polyalkylene ether polyol having an oxyethylene chain content of 20 to 100% by weight, which is exemplified as the constituent raw material of the urethane polymer, is used. Those listed as (b1), [II]
Active hydrogen-containing compounds and organic amine compounds exemplified above (for example, alkylenediamine having 2 to 6 carbon atoms (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.); polyalkylene (having 2 to 6 carbon atoms)
Polyamines [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, methylaminopropylamine, methyliminobispropylamine, etc.]; alicyclic or heterocyclic polyamines Class (C4-15) [N-aminoethylpiperazine, 1,3-diaminocyclohexane,
Isophoronediamine, hydrogenated methylenedianiline, etc.];
Aliphatic polyamines having an aromatic ring (8 to 1 carbon atoms)
5) [Xylenediamine, tetrachloro-p-xylenediamine, etc.]; Aromatic polyamines (having 6 to 2 carbon atoms)
0) [phenylenediamine, toluenediamine, methylenedianiline, diaminodiphenylsulfone, benzidine, thiodianiline, methylenebis (o-chloroaniline), m-aminobenzylamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, etc. ]; Alkanolamines (triethanolamine, methyldiethanolamine, etc.); Monoamine (butylamine,
Octylamine, etc.) to which an alkylene oxide having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, butylene oxide, and their combination, etc.) is added (blocking or random addition may be made when used in combination).

When the polyol (b2) has a high molecular weight,
It becomes water-soluble by introducing an oxyethylene chain into the molecule.
When it has a low molecular weight, it is water-soluble by itself. The average molecular weight of the polyol (b2) is usually 200 to 15,000,
It is preferably 300 to 10,000. The number of functional groups is
It is usually 2 to 8, preferably 2 to 4.

As the catalyst (C), dibutyltin dilaurate, alkyl titanate, organosilicon titanate, stannas octoate, lead octylate, zinc octylate,
Metal-based catalysts such as bismuth octylate, bismuth neodecanoate, dibutyltin diorsophenylphenoxite, reaction products of tin oxide and ester compounds (such as dioctyl phthalate); monoamines [triethylamine etc.], diamines [N, N, N ', N'-tetramethylethylenediamine, etc.], triamines [N, N,
N ′, N ″, N ″ -pentamethyldiethylenetriamine and the like], amine catalysts such as cyclic amines [triethylenediamine and the like], and the like. These catalysts are 2
You may use it in combination of 2 or more types. The type and blending amount of the catalyst can be selected according to the purpose, and the blending amount is usually 0.1 to 10 parts by weight, preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the urethane elastomer. Particularly in the case of a metal catalyst, if it exceeds 10 parts by weight, the heat resistance is deteriorated, which is not preferable.

The weight ratio of water to the polyol (b2) in the curing agent is usually 10:90 to 95: 5, preferably 30 :.
70-95: 10. If the water ratio is less than 10, the adhesive strength will be insufficient, and if it exceeds 95, the cured adhesive will have a high elastic modulus and lack flexibility.

In the bonding method of the present invention, the mixing ratio of the main agent and the curing agent is usually 10 to 100 parts by weight of the main agent.
It is 300 parts by weight. If the amount of the curing agent is less than 10 parts by weight, the elastic modulus becomes high, and if it exceeds 300 parts by weight, the adhesive strength becomes insufficient.

As the method for producing the main agent, for example, the organic polyisocyanate compound (a) and the polyol (b1) are reacted in the presence of the water-soluble diluent (B) at a reaction temperature of 60 to 110 ° C.
The method of reacting for 3 to 12 hours can be mentioned.

Examples of the method for producing the curing agent include a method of mixing water, the polyol (b2) and, if necessary, a catalyst at room temperature to 50 ° C.

In the present invention, the method of applying the adhesive to the adherend is not particularly limited, but at least one surface of the adherend, preferably the surface of the porous material, may be scraped or brushed. Application method, application method to the adherend through a nozzle after mixing with a two-liquid mixing machine, collision mixing type spray machine such as air mixing type two-head gun type airless spray machine or collision mixing chamber type gun type airless spray machine The method of applying may be mentioned. Among these, a preferred method is a method of coating with a collision-mixing type spray machine which provides good workability. In particular, in the bonding method of the present invention, the adhesive has a low viscosity,
Since it has features such as instant compatibility and a wide allowable liquid ratio of the main agent and the curing agent, there is a great advantage in that a two-head gun sprayer that is inexpensive, compact, simple, and has good working efficiency can be used.

The pressing conditions in the bonding method of the present invention are not particularly limited, but usually the temperature is 15 ° C to 80 ° C,
The pressure is 0.1 to 10 Kg / cm ² , and the time is 5 seconds to 10 minutes.

[0026]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In the following,
Parts are parts by weight,% is% by weight, and ratios are weight ratios. The meanings of the abbreviations in the examples and the evaluation test methods are as follows. (Symbol) PEG-2000: Polyoxyethylene glycol [molecular weight = 2000] 70-3000: Random addition of ethylene oxide and propylene oxide to ethylene glycol [molecular weight = 3000, oxyethylene chain content = 70% by weight] 80 -4000: Random addition of ethylene oxide and propylene oxide to ethylene glycol [molecular weight = 4000, oxyethylene chain content = 80% by weight] G-3000: Random addition of ethylene oxide and propylene oxide to glycerin [molecular weight = 32
00, oxyethylene chain content = 70% by weight] AP-470: propylene oxide adduct of triethanolamine [molecular weight = 470] PM-200: polyethylene glycol (molecular weight 20
0) methyl ether compound PM-400: polyethylene glycol (molecular weight 40
0) Methyl etherified compound MDI: 4,4′-diphenylmethane diisocyanate cat-U: amine catalyst [trade name; UCAT-100
0, manufactured by San Apro Co., Ltd.]

(Evaluation Test Method) 1. Instantaneous compatibility: See whether or not the main agent and the curing agent adjusted to 30 ° C. are mixed at a specified mixing ratio and are instantly compatible.
(Display: ◎ = instantly compatible, △ = instantly compatible,
X = not compatible) 2. Tack free time (TFT): A main agent and a curing agent whose temperature are adjusted to 30 ° C. are mixed at a prescribed mixing ratio, and the time when tack disappears is measured. (Unit = second) 3. Adhesive strength development time: Adhere the canvas and canvas with an adhesive,
The time when the peel adhesion strength becomes 300 g / 25 mm or more is measured. (Unit = second) 4. Adhesive strength: 180 ° peel strength (tensile speed = 100m
m / min). (Unit = Kg / 25 mm) 5. Adhesive state: Material break = adherend breakage, interface = interface peeling. 6. Flexibility: The elastic modulus of a film obtained by curing an adhesive is measured. (Display: ◎ = soft, △ = slightly hard, × = hard)

Production Examples 1 to 4 [Production of Main Agent] An organic polyisocyanate compound (a), a polyol (b1) and a water-soluble diluent (B) shown in Table 1 were charged in a 4-necked Kolben and the mixture was heated at 90 ° C. for 5 The main ingredients <1> to <4> of the present invention were obtained by reacting for a time.

[0029]

[Table 1]

Production Examples 5 to 7 [Production of curing agent] A 4-necked Kolben was charged with the components shown in Table 2 at 25 ° C.
Then, the mixture was stirred and mixed for 10 minutes to obtain the curing agents [1] to [3] of the present invention.

[0031]

[Table 2]

Examples 1 to 5 A main agent and a curing agent having a part ratio shown in Table 3 were spray-coated on urethane foam with an air-impingement mixing type two-head gun type airless sprayer, and the cushion was immediately applied. The cloth cloth material for wood was pressed for 60 seconds at a pressure of 200 g / cm ² . The adhesion was measured after curing for 5 minutes at room temperature. At the same time, Table 3 shows the results of making and testing samples for instantaneous compatibility, TFT, adhesive strength development time, and flexibility test.

[0033]

[Table 3]

Examples 6 to 9 A base material and a curing agent having a part ratio shown in Table 4 were spray-coated on a urethane foam with a collision mixing chamber type two-liquid high-pressure airless sprayer at the coating amounts shown in Table 4 and immediately the cushioning material was used. 60% of cloth material for skin at a pressure of 200 g / cm ^2.
Pressed for 2 seconds. The adhesion was measured after curing for 5 minutes at room temperature. At the same time, instantaneous compatibility, TFT, adhesive force development time,
Table 4 shows the test results obtained by making samples for the flexibility test.

[0035]

[Table 4]

COMPARATIVE EXAMPLE 1 In a 4-necked Kolben, 711 parts of 70-3000 and M
289 parts of DI was charged and reacted at 90 ° C. for 5 hours to obtain a main agent having a viscosity of 2950 cps / 30 ° C. In the same manner as in Example 1, the main ingredient adjusted to 30 ° C. and water were mixed at 10:
Spraying was carried out at a compounding ratio of 5, but as shown in Table 5, the viscosity of the main component was too high to be sprayed.

Comparative Example 2 A 4-necked Kolben was charged with 685 parts of PP-2000 and M.
315 parts of DI was charged and reacted at 90 ° C. for 7 hours to obtain a main agent having a viscosity of 3750 cps / 30 ° C. In the same manner as in Example 1, the main ingredient adjusted to 30 ° C. and water were mixed at 10:
Spraying was carried out at a compounding ratio of 5, but as shown in Table 5, the viscosity of the main component was too high to be sprayed.

Comparative Example 3 A four-necked Kolben, 480 parts of PP-2000, PM-
Charge 300 parts of 400 and 220 parts of MDI,
The reaction was performed at 0 ° C for 7 hours to obtain a main agent having a viscosity of 920cps / 30 ° C. In the same manner as in Example 1, this main agent adjusted to 30 ° C. and water were sprayed at a mixing ratio of 10: 5.
As shown in Table 5, the base resin and the curing agent were not compatible and were not cured.

Comparative Example 4 Adhesive strength was measured by coating the main agent <2> and water at a compounding ratio of 10: 5 at the coating amounts shown in Table 5. At the same time, instant compatibility,
Table 5 shows the test results obtained by preparing samples for the TFT, the adhesive force development time, and the flexibility test.

[0040]

[Table 5]

As is clear from Table 3, Table 4 and Table 5, the bonding method of the present invention is excellent in sprayability, instantaneous compatibility and adhesive force manifestation, and has excellent adhesive strength and flexibility of the bonded product. .

[0042]

EFFECTS OF THE INVENTION In the method for adhering a porous material according to the present invention, the main component of the adhesive and the curing agent have instantaneous compatibility and the viscosity is low, so that spray coating can be easily performed with a simple spray device. It is a bonding method with extremely good work efficiency. Further, it has the effects of being fast-curing, exhibiting sufficient adhesive strength in a short time with a small amount of application, having high adhesive strength, and being flexible in the adhesive layer. In addition, it has excellent fogging properties and does not cause air pollution caused by organic solvents. Because of the above effects, the method for adhering a porous material of the present invention is particularly useful for manufacturing interior parts such as automobile seats and door trims, and for manufacturing wall materials and floor materials.

Front page continuation (72) Inventor Hajime Akiyama 1-11, Hitotsubashi-honcho, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd. (56) Reference JP-A-58-52378 (JP, A) JP-A-5-171774 (JP, A) JP-A 2-60983 (JP, A) JP-A 5-140339 (JP, A) Fujimoto Takehiko, Introduction to New Surfactants, Sanyo Kasei Kogyo Co., Ltd., October 31, 1981, 89-126 (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09J 4/00-201/10

Claims (3)

(57) [Claims] 1. When adhering adherends of which at least one is porous, the following main agent and curing agent main agent: an organic polyisocyanate compound (a) and an oxyethylene chain are attached to the surface of at least one of the adherends. A urethane prepolymer (A) derived from a polyalkylene ether polyol (b1) having a content of 20 to 100% by weight, and the following general formula (1) or
One or more compounds represented by (2) that do not contain active hydrogen
Comprising a water-soluble diluent mixture of (B). Curing agent: a mixture of water, a water-soluble polyalkylene ether polyol (b2) and optionally a catalyst (C) [with water
The weight ratio of (b2) 10: 90~95: 5 ] Tona Ri main agent
The mixing ratio of the curing agent and the curing agent is 100 parts by weight of the main agent and the curing agent is
0-300 After applying the parts der Ru two-component curable solventless adhesive, a bonding method of a porous material, characterized in that the push-out adhesive overlay them. Formula ^{X [O- (R 1 O)} n -R 2] m (1) X in _{^{[O- (R 1 O) n}} -OC-R 2] m (2) [ wherein, X is an alcohol, a polyhydric Alcohol, alkano
OH of luamine, phenol and bisphenol A
Excluded groups, R ¹ is an alkylene group having 2 to 4 carbon atoms, and R ² is carbon.
Alkyl groups or phenyl groups having 1 to 18 primes (halogen
Or even if it is substituted with an alkyl group having 1 to 18 carbon atoms
Good. ), N is an integer of 1 to 40, m is an integer of 1 to 8
You ] 2. The bonding method according to claim 1, wherein the amount of (B) in the main agent is 3 to 70% by weight . 3. The bonding method according to claim 1, wherein the two-component curable solventless adhesive is applied by a collision mixing type spray machine.