JP3288151B2 - Two-component polyurethane foam-type sealing material composition, sealing method and lamp - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-component polyurethane foam-type sealing material composition which has no contamination to a transparent polycarbonate resin or a transparent acrylic resin and has good heat-resistant permanent set characteristics. More specifically, the present invention relates to a two-component polyurethane foam-type sealing material composition having high heat resistance and chemical resistance, which is used for various sealing materials such as lamps for vehicles and the like, and sealing materials for refrigerators.

[0002]

2. Description of the Related Art Foaming is carried out by mixing a base liquid composed of a polyol, a catalyst, a foaming agent, a foam stabilizer and the like with a curing agent liquid composed of a polyisocyanate and / or a modified polyisocyanate having at least two terminal isocyanate groups. It is widely known that a two-component polyurethane foam obtained by forming a sealed sealing material is useful as a sealing material because of its excellent elasticity, durability and abrasion resistance. Regarding the two-component urethane type sealing material, JP-B-60-49239 and JP-B-59-3703 are disclosed.
6, Japanese Patent Publication No. 1-38152, JP-A-2-298574,
Japanese Patent Publication No. 3-33756, Japanese Patent Application Laid-Open No. 4-185657, and Japanese Patent Publication No. 4-63912.

[0003] Depending on the shape of the sealing surface, the sealing material is not suitable for a preformed product, but may be discharged, cast, foamed, and cured and molded directly on the sealing surface. Examples of the hermetic seal are a bent lamp housing used for automotive lighting and a lens sealing part fitted to it, a fender sealing part for a vehicle, a sealing part for a window glass of a vehicle, and a wall fitting part for an aluminum sash for building materials. And sealing of sealing parts for the purpose of preventing water leakage or preventing water leakage in many other building material fields. In general, a two-component polyurethane-based sealing material composition is injected or discharged into a predetermined site by using a mixing and injection machine, and is appropriately foamed and cured on the surface of the object within a relatively short time to directly seal. It is known that it can exert its function.

[0004] In the conventional two-component polyurethane foam type sealing material composition, there is a problem of contamination of polycarbonate or acrylic material and the compression set in an environment of 90 to 110 ° C is extremely high. There were major issues such as lack of high-temperature long-term seal reliability. Also,
When the sealing surface is a highly uneven surface, slope, vertical surface, etc., when discharging with an injection machine, liquid dripping occurs before the sealing material foams and hardens, ensuring a predetermined thickness and a predetermined amount Had no shortcomings. That is, with respect to the conventional two-component polyurethane foam-type sealing material composition, there are major problems such as a problem of contamination of polycarbonate and acrylic materials, a problem of suppressing (relaxing) the generation of compression set in an environment of about 100 ° C. The occurrence of liquid dripping on an inclined surface, etc., has three main issues.

The above problem will be described in more detail.
It is as follows. 2. Description of the Related Art In recent years, in order to reduce the weight and functionality of automobiles, lightweight and transparent polycarbonate or acrylic resin has been frequently used instead of heavy glass. However, in the conventional two-component polyurethane-type sealing material composition, during or after the curing, some component diffuses or bleeds from the sealing material, which adheres to and impregnates the surface of the target material, and becomes cloudy, cracked, Alternatively, problems such as deformation and destruction occur. Also, when lighting a vehicle lamp, the ambient temperature of the sealing material is 1
The temperature is as high as around 00 ° C and the compression set is 100
%, The sealability is impaired. In addition, when using a sealing material that is generally formed by injection molding using an injection machine, if liquid dripping occurs during the discharge of the composition, the upper part of the discharge becomes thinner and the lower part becomes thicker, so that the sealing function is totally reliable. It was a cause of lack of sex.

In order to solve the liquid dripping as much as possible, it is necessary to add and use colloidal silica, bentonite, carboxylic acid or alcohol-treated calcium carbonate as a thixotropic modifier to a two-component polyurethane foam type sealing material. Are known. However, these inorganic thixotropic modifiers generally require an extremely large amount of addition to exert their effects sufficiently, so that the apparent viscosity of the system significantly increases, and curing due to poor mixing occurs. There are problems such as failure, clogging of the nozzle of the injector, and instability during storage.

Recently, in order to obtain a two-component polyurethane foam-type sealing material composition which does not cause liquid dripping, which is the first problem, it has been proposed to use aliphatic monoamines and aliphatic diamines as thixotropic agents in Japanese Unexamined Patent Publication (Kokai) No. Hei 10 (1994). It is disclosed in 5-1273. However, according to this technology, the liquid dripping property on the inclined surface can be solved to some extent, but the second major problem is the contamination to polycarbonate and acrylic materials and the third problem.
It has been found that the problem of permanent set of compression or elongation under high temperature environment, which is the subject of the above, remains. That is, since the thixotropic agent of the disclosed technology generally shows a high vapor pressure at relatively room temperature, it is presumed that the amine compound is diffused to the surroundings and contaminates the material until curing or due to heat generation during curing. Was. Particularly, the limit value of the reliability of the heat-resistant seal of the composition according to the disclosed technique is as low as 70 ° C. at most from the state of the occurrence of permanent strain.

[0008]

SUMMARY OF THE INVENTION In view of the above, the present invention solves the following two important problems which are strongly demanded in the sealing market, and has three problems depending on the substance of the adherend. It is an object of the present invention to provide a two-component polyurethane foam-type sealing material composition which solves the problems of the eyes at the same time, has excellent storage stability, and is excellent in injection workability such as rich uniform mixing properties. That is, the objects of the present invention are: After the urethane sealing material obtained by the water foaming technique is left in a compressed state at 100 ° C. and 50% for 22 hours, the compression set measured after releasing the load is at most 40% or less; 2. No contamination to transparent materials such as polycarbonate and acrylic. An object of the present invention is to provide a two-component polyurethane foam-type sealing material composition which does not generate liquid dripping from the time of discharge and application to the time of foaming and curing, and has good work stability of a discharge machine.

[0009]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and have found that a polyol, a catalyst, a water blowing agent, a silicone-based foam stabilizer, a thixotropic agent, and a permanent distortion improver are used. And a curing agent liquid comprising a polyisocyanate and / or a modified polyisocyanate having at least two or more terminal isocyanate groups (b)
A so-called two-component polyurethane foam-type sealing material composition comprising: a main agent liquid (a) containing a predetermined amount of a polyvalent mercapto compound as a thixotropic agent; The present inventors have found that the above-mentioned problems can be solved by adding a predetermined amount of a halogen-based thermoplastic resin in the rubber region at room temperature having a polymer primary particle diameter of 2 μm or less at most as a permanent set improver for compression or elongation. The invention has been completed.

That is, according to the present invention, 0.0001 to 3 parts by weight of a catalyst and O.O. of a water blowing agent are added to 100 parts by weight of a polyol having a total weight average hydroxyl value in the range of 10 to 150 mgKOH / g. 1 to 1 part by weight, 0.1 to 3 of foam stabilizer
1 to 5 parts by weight, permanent set improver for compression or elongation
Curing comprising a main agent liquid (a) containing 0 parts by weight, 0.001 to 0.20 gram equivalent of a thixotropic agent, and a polyisocyanate and / or a modified polyisocyanate having at least two or more terminal isocyanate groups. The solution (b) was mixed with 100 parts by weight of (a) and 1 part of (b)
In a two-component polyurethane foam-type sealing material composition which is mixed and used so as to have a mixing ratio of 0 to 300 parts by weight, a permanent distortion improving agent for compression or elongation in the base material liquid (a) contains a polymer primary particle. The present invention relates to a two-component polyurethane foam-type sealing material composition, which is a halogen-based thermoplastic resin having an average diameter of 2 μm or less at most and containing a polyvalent mercapto compound as a thixotropic agent.

Preferably, the polyol has the following (A)
(C), wherein the polyol has a total weight average hydroxyl value of 20 to 80.
The two-component polyurethane foam-type sealing material composition used in the range of mgKOH / g, and thus the foam obtained is soft having a rubber hardness of JIS-A of 20 or less. (A) Polyether polyols (B) Polymer polyols (C) Polyester polyols

[0012] The halogen-based thermoplastic resin as a permanent distortion improving agent for compression or elongation is vinyldene chloride resin, vinylidene fluoride resin, vinyl chloride resin, vinyl fluoride resin, monochlorovinyl acetate resin, chlorinated polyethylene, chlorinated polyethylene, Selected from the group consisting of modified polypropylene and mixtures thereof.
It is preferable to use it in the range of weight%.

As the thixotropic agent, the polyvalent mercapto compound is selected from aliphatic mercaptoglycerols, aliphatic dimercapto compounds, aliphatic trimercapto compounds, aliphatic tetramercapto compounds and mixtures thereof. (A) It is highly preferred to use at least 0.005 gram equivalents per 100 parts by weight.

In the two-component polyurethane foam-type sealing material composition according to the present invention, the base liquid (a) is basically a composition containing a polyol as a base resin, and the present invention is particularly restricted in terms of workability. However, the static viscosity of the base solution (a) is preferably 50,000 cps or less at most at 25 ° C., particularly preferably 100 cps or less.
~ 20,000 cps, more preferably 10
The range of 0 to 5,000 cps is good.

The curing agent liquid (b) is basically a polyisocyanate or a modified polyisocyanate containing two or more active isocyanate groups in one molecule, and the system has a melt viscosity of 50,000 cps or less, preferably Is 2
000 cps or less, isocyanate content of 5 to 3
Those in the range of 8% by weight are preferred. Representative polyisocyanates include, for example, tolylene diisocyanate,
Hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, polymeric polyisocyanate called crude MDI, hydrogenated diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, isophorone diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate Representative examples include polyisocyanates, polynuclears thereof, and mixtures thereof. The modified polyisocyanate is a so-called urethane prepolymer containing two or more isocyanate groups in one molecule derived from the above-mentioned polyisocyanate and the following polyol.
One or two or more of them can be used in combination.

More preferable curing agents include polyisocyanates such as diphenylmethane diisocyanate, polynuclear diphenylmethane diisocyanate, orthotrizine diisocyanate, 1,5-naphthalene diisocyanate, tolylene diisocyanate, and polynuclear tolylene diisocyanate, and the aromatic diisocyanate and polyol. And modified polyisocyanates represented by urethane prepolymers whose terminal functional groups are derived from two or more isocyanate groups.

The polyol which is a base component of the main component liquid (a) has a total weight average hydroxyl value of 10 to 150 m
gKOH / g, preferably 20-80 mgKOH
/ G is important in the present invention. The total weight average hydroxyl value of the polyol is 150 mg KO
If it is not less than H / g, it is hard and brittle, and only a hard foam sealing material can be obtained, causing a problem that crack resistance and elongation sealing properties are significantly lacking.

Although the present invention is not particularly limited, the polyols represented by the following (I) to (XIV) are typical, and usually one or a combination of two or more thereof is used. , The total weight average hydroxyl number of which is used as the range of the values described above. (I) ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin,
Polyhydric alcohols such as pentaerythritol, trimethylolpropane, sorbitol, and sucrose. (II) An alkylene oxide adduct such as ethylene oxide or propylene oxide having a hydroxyl value of 10 to 560 mgK with respect to the polyhydric alcohol of the above (I).
Polyether polyols in the range of OH / g.

(III) Bisphenol A, Bisphenol F, resole type phenolic resin obtained from phenol and formalin, resole type xylene resin, terpene
A hydroxyl value of 10 to 560 mg KO obtained by adding a so-called alkylene oxide represented by ethylene oxide or propylene oxide to a known polyhydric phenol represented by a bisphenol copolymer resin or the like.
Polyether polyols appropriately prepared in the range of H / g.

(IV) The above-mentioned polyhydric alcohols (I) and aliphatic or aromatic di-, tri-, or tetracarboxylic acid compounds and their anhydrides or their methyl, ethyl,
Polyester polyols having at least two or more hydroxyl group terminals derived from lower alkyl esters such as propyl and butyl, and polyester polyols derived from caprolactone ring-opened adducts. (V) Polyester polyols prepared by dehydration polycondensation of aliphatic hydroxycarboxylic acids or aromatic hydroxycarboxylic acids with polyhydric alcohols. (VI) The hydroxyl value obtained by further adding an alkylene oxide such as ethylene oxide or propylene oxide to a low molecular weight compound having a weight average molecular weight of 3,000 or less of the polyester polyol of (IV) to (V) is 10 to 10.
Polyester polyether block polyols in the range of 560 mg KOH / g.

(VII) an unsaturated monomer (i) having an acryloyl or methacryloyl group and a hydroxyl group,
An unsaturated monomer having an isopropenyl group or a vinyl group and a hydroxyphenyl group (ii), having a weight average molecular weight of 3,
(I) and / or (ii) of a so-called macromonomer (iii) having a softening point of 80 ° C. or more and a softening point of 80 ° C. or more, and if necessary, further (iii) in an amount of 10% by weight in the monomer component % And other acrylic unsaturated monomers copolymerizable with those unsaturated monomers (ii.
i) and a polymerization initiator, if necessary, a chain transfer agent or the like, and a weight average molecular weight expressed in terms of polystyrene by GPC measurement in the range of 1,000 to 50,000,
Acrylic polyols having an average of two or more hydroxyl groups introduced into one molecule and having a glass transition temperature of the main chain of 0 ° C. or less.

(VIII) Polybutadiene-based polyols (alias: polybutadiene hydroxide) and / or saturated polyolefin polyols obtained by hydrogenating the same. (IX) Polyisoprene-based polyols (alias: polyisoprene hydroxide) and / or saturated polyolefin polyols obtained by hydrogenating the same. (X) Methyl and / or phenylpolysiloxane-based polyols. (XI) Dimer acid-modified polyols. (XII) Castor oil-modified polyols. (XIII) In the presence of the polyether polyol, acrylonitrile, styrene, and an ethylenically unsaturated monomer represented by methyl acrylate are added together with an azo radical initiator or a peroxide at a temperature of 130 to 230 ° C. Modified polymer-grafted polyether polyols in which an acrylic thermoplastic resin is precipitated and dispersed and stabilized by graft polymerization. These are referred to as polymer polyols, but in the present invention, those obtained by subjecting a halogen-based monomer to a graft polymerization operation are excluded. (XIV) Polycarbonate polyols.

In the present invention, when two or more of the above-mentioned polyols are used in combination, they may be mixed and used arbitrarily within a range that does not cause layer separation at room temperature in consideration of their mutual compatibility. It is needless to say that the hydroxyl value is used within the scope of the invention. Particularly preferred polyols (A) to (C) of the present invention are (A) polyether polyols described in (II) to (III) above, and (B) polymer polyols described in (XIII) above, (C) ) Polyester polyols refer to (IV) to (VI). In the polyol of the present invention, when a polyol having a weight average molecular weight of less than 1,000 described in the above (I) to (XIV) is used, the same applies as long as the hardness of the final urethane foam sealing material does not become too high. It is important to use together with other polyols having a weight average molecular weight of 1,000 or more described in the above (I) to (XIV), and generally, the total polyol has a molecular weight of 500 or more.
The following low molecular weight polyols are preferably contained within 10% by weight, more preferably within 5% by weight. When used in an amount of 10% by weight or more, the foam tends to be considerably hard, and thus tends to lack elongation characteristics and bending characteristics, which is not preferable. More preferably, the total weight average molecular weight of the total polyol consisting of one or more kinds is approximately 2,000 to 100,0.
00 range, most preferably 2,000-5,000.
It is highly preferred to use in the range of 0.

The permanent distortion improving agent for compression or elongation, which is added to the liquid of the main component (a) of the present invention, is a fine particle of halogen-based thermoplastic resin in a rubber region at room temperature with at most primary particles of 2 μm or less on average. Body. The finely divided halogen-based thermoplastic resin is used as one of the main components (a) of the two-component polyurethane foam-type sealing material composition, whereby 100% of the urethane foam finally obtained is obtained.
At the time of heating compression load around ℃, the remarkable effect of suppressing and relaxing the distortion generation factor of the rearrangement bond due to the urethane hydrogen bond and the rearrangement of the alphanate bond, for unknown reasons, It has been found by the present inventors. Therefore, it was concluded that it could be used as a permanent set improving (suppressing) agent (also referred to as a strain relaxation suppressing agent). In particular, 100
It is characterized by a remarkable reduction in the rate of generation of permanent heating compressive strain or elongation permanent strain at about ° C, and there has been no recognition that such an effect is exhibited conventionally. Preferably,
The primary particle size is preferably 1 micron or less, and more preferably 0.1 to 0.5 micron from the viewpoint of surface gloss and smoothness of the cured foamed sealing material.

In order to sufficiently exhibit the above-mentioned functions and effects, the amount of the halogenated thermoplastic resin is preferably in the range of 0.1 to 35% by weight, more preferably 1 to 20% by weight in (a). is there. If the content is less than 0.1% by weight, a sufficient effect cannot be expected.
If it is used in excess of 5% by weight, the system will have a significant thickening, solidification and clogging at the injection nozzle, a problem of a significant lack of chemical resistance, other problems such as cell roughness and severe roughening of the cured surface, despite the action hardening. Is conspicuous.

The thermoplastic resin includes, for example, vinyl chloride resin, vinyl fluoride resin, vinylidene chloride resin, vinylidene fluoride resin, chlorosulfonated polyethylene resin, monochlorovinyl acetate resin, chlorinated polyethylene,
Examples thereof include chlorinated polypropylene and mixtures thereof, and those having a molecular weight of 5,000 or more are generally preferred. Vinyl chloride resin and vinylidene chloride resin are inexpensive and preferable. The present invention also encompasses a dispersion-stabilized halogen-based thermoplastic resin in a grafted state.

There are no particular restrictions on the method for producing these fine particle resins. For example, a product obtained by an ordinary emulsion polymerization method or the like, or a so-called acrylic polymer graft polyol represented by the above, may be used. The particles may be particles obtained by nonaqueous dispersion polymerization of a halogen-containing unsaturated monomer using a medium in a polyol or a low-boiling solvent, and any method for preparing fine particles may be employed. In particular, when the fine particles having a size of 1 micron or less are prepared in advance, those obtained by a known emulsion method or non-aqueous dispersion method are easily adapted. In the method of dispersing in (a), for example, a method may be used in which an emulsion of a halogen-based thermoplastic resin is slowly added to the solution (a) and then desolvation or dehydration is performed. . (A) In the case where the dispersion state of the permanent distortion improver component in the liquid is slightly unstable, for example, a peroxide may be added to the same system to secure stability in the grafting reforming reaction, or the like. Alternatively, a secondary stabilizing means such as improving the dispersion stability by appropriately adding a small amount of a known dispersing aid, a surfactant or a compatibilizing alloying aid which is soluble in a known polyol component and preferably improving the dispersion stability is preferably employed. You can In addition, a radical polymerization reaction using the resin raw material monomer is performed in the polyol component, and the resin is stably deposited, dispersed, and formed into an added state while appropriately causing graft polymerization. A method of dispersing and adding in an amount can also be preferably employed as a means for adding the fine particles of the thermoplastic resin of the present invention.

The polyvalent mercapto compound used as the thixotropic agent added to the main ingredient (a) of the present invention includes aliphatic mercaptoglycol compounds, aliphatic dimercapto compounds, aliphatic trimercapto compounds, aliphatic tetramercapto compounds And mixtures thereof. More specifically, the thiol group has at least 2
Or an aliphatic mercapto compound containing one or more active hydrogen functional groups capable of reacting with a thiol group and an isocyanate group in the same molecule, respectively. There are no compounds, but the following compounds are mentioned as typical examples.

Examples of the former which are aliphatic mercapto compounds containing at least two or more thiol groups in one molecule include triglycol dimercaptan, trimethylolpropane tris (thioglycolate), and trimethylolpropane tris (β -Thiopropionate), pentaerythritol tetra (thioglycolate), and pentaerythritol tetra (β-thiopropionate). In addition, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, butylene glycol,
Neopentyl glycol, glycerin, sorbitol,
For one type of active hydroxyl group of a polyhydric alcohol such as sucrose, a thiol group is obtained at the end obtained by an aliphatic mercaptocarboxylic acid such as mercaptoacetic acid or mercaptopropionic acid in the same amount as the active hydroxyl group. A polyhydric mercaptoester derived from two or more polyhydric alcohols. Still further, succinic acid,
Obtained from dicarboxylic acids such as succinic anhydride, adipic acid, maleic acid, maleic anhydride and fumaric acid, polycarboxylic acids such as pentaerythritol tetraacetate, and so-called mercapto alcohols such as mercaptoethanol, mercaptopropanol and mercaptobutanol. Is a polyvalent mercaptoester.

As an example of the latter, an aliphatic mercapto compound containing one or more thiol groups and another active hydrogen functional group capable of reacting with an isocyanate group in the same molecule is thioglycerol and the like. As particularly preferred examples, those relatively easily available include trimethylolpropane 1 mol equivalent and 3 mol equivalent of mercaptopropionic acid or an ester with mercaptoacetic acid, pentaerythritol 1 mol equivalent and 4 mol equivalent of mercaptopropionic acid. Or esters with mercaptoacetic acid, thioglycerol and the like. The polyvalent mercapto compound of the present invention preferably has a saturated vapor pressure at 50 ° C. of 10 hp.
a) It is highly preferable to select and use as shown below from the viewpoint of stain resistance to polycarbonate, acrylic, and the like.

The polyvalent mercapto compound used as the thixotropic agent of the present invention is used in an amount of 0.001 to 0.20 gram equivalent or more, preferably 0.005 to 0.15 gram equivalent, per 100 parts by weight of the polyol. By using in this range, liquid dripping prevention from the time of injection and discharge to the time of foaming hardening can be obtained. The upper limit of the addition amount varies depending on the type of the polyvalent mercapto compound, and as described above, is preferably about 0.2 gram equivalent or less. If it is more than this, the nozzle discharge operation stability is somewhat marginalized.

In the present invention, the main component liquid (a) comprising a polyol, a catalyst, water as a foaming agent, a silicone-based foam stabilizer, an agent for improving compression or elongation, a thixotropic agent, and a polyisocyanate And / or at least 2
And a curing agent liquid (b) comprising a urethane prepolymer having two or more terminal isocyanate groups in a mixing ratio (b) /
(A) = 10 to 300 parts by weight / 100 parts by weight, and / or molar equivalent ratio (b) / (a) = 0.9 to 1.1 mol / 1
The reason why the two-component polyurethane foam-type sealing material composition is mixed and used in a molar amount is as follows. That is, the reason for setting the mixing ratio of 10 to 300 parts by weight of (b) with respect to 100 parts by weight of (a) is that the two-component polyurethane foam of the present invention is used in view of the performance of a general commercially available mixing and discharging machine. The mold sealing material composition is within a range that allows accurate and complete uniform mixing. The reaction ratio of the active hydrogen of (a) to the active isocyanate group of (b) is 1:
The reason why the equivalent ratio is set to (0.9 to 1.1) is that if the equivalent ratio is exceeded, lack of chemical resistance, remarkable lack of weather resistance and poor heat resistance rigidity of the foamed sealing material occur.

As the catalyst of the liquid (a) of the present invention, as a polyurethane foam catalyst, for example, an organotin compound represented by dibutyltin dilaurate, dioctyltin dimaleate, stannous octylate, dibutyltin oxide, or a tetrabutyltin oxide Organic titanate compounds represented by butyl titanate,
Organometallic curing catalysts such as lead naphthenate and lead octylate,
Further, for example, triethylenediamine, N-methylmorpholine, N, N'-dimethylbenzylamine, N, N '
A tertiary amine catalyst such as dimethylethanolamine,
1,8-diaza-bicyclo [5,4,0] undecene-
7 (DBU) or an aromatic sulfonate-based catalyst thereof,
A curing control cocatalyst such as di-n-butyl phosphate or ricinoleic acid, which may have 10 to 28 carbon atoms and which may have higher aliphatic saturated or the same unsaturated carboxylic acid, is used alone or in any combination. can do. In the case of the present invention, as a particularly preferred catalyst for the liquid (a), as an organometallic catalyst, dibutyltin dilaurate is used in the liquid (a) in a range of 10 to 2000 ppm and a tertiary amine catalyst which is non-volatile at ordinary temperature. (A) triethylenediamine as
It is preferable to use 0.05 to 1% by weight in the liquid.

In the present invention, the foaming agent of the solution (a) of the present invention is water, and the amount of water used in the foaming agent is 0.2% in (a).
It is used at a rate of １1% by weight. If the amount of water used is 1% by weight or more, it is difficult to ensure the water leakage prevention of the obtained foamed sealing material, and if it is 0.2% by weight or less, only a low foam is obtained and the foam function as a sealing agent is not exhibited. It is. As a urethane foaming agent other than the water foaming agent, for example, a low-boiling hydrocarbon solvent or a low-boiling halogenated hydrocarbon may be used in combination in a very small amount. For example,
Examples of the low-boiling hydrocarbon solvents include n-hexane and n-heptane. In the low boiling halogenated hydrocarbon,
Examples include trichloromonofluoroethane, dichlorofluoromethane, monochlorodifluoromethane, dichlorotetrafluoroethane, methylene chloride, trichlorotomefluoroethane, and trichloroethane.

The foam stabilizer used in the liquid (a) is a foam stabilizer for urethane foaming, and is preferably, for example, a silicon-based surfactant compound. As the silicon-based surface active compound, R ₃ SiO— (SiR ₂ O) x—SiR ₃ (where R represents an alkyl group such as a methyl group, an ethyl group, or a butyl group, or an aryl group such as a phenyl group; x represents an integer.), but such a foam stabilizer is not preferred in the present invention because it has poor compatibility with polyol and lacks storage stability. The silicon-based surface active compound usable as the foam stabilizer of the present invention includes, for example, a compound represented by the general formula (1): (Wherein R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ′ represents a divalent organic group, n represents an integer of 2 to 4, and x, y, and z each represent 1 or more. An organosilicon-terminal hydroxyl group type alkylene oxide copolymer represented by the following general formula (2): (Where R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ′ represents a divalent organic group, R ″ represents an alkyl group having 1 to 4 carbon atoms, and n represents 2 to 4 carbon atoms. Integers are represented by x, y,
z represents an integer of 1 or more. ), An organosilicon-terminal alkoxy-modified alkylene oxide copolymer, or (Wherein R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ′ represents a divalent organic group, and R ′ ″ represents an isoalkyl group having 7 to 35 carbon atoms or 1 carbon atom. And n represents an integer of 2 to 4, and x, y, and z each represent an integer of 1 or more.) An organosilicon-terminal ester-modified alkylene oxide copolymer represented by the following formula: Any one of which is 0.5 to 3% by weight in the base liquid (a).
It is preferable to contain in the range of. Among them, a preferred foam stabilizer of the present invention is an iso-higher fatty acid ester of an organosiloxane-alkylene oxide copolymer represented by the general formula (3). These foam stabilizers convert the hydroxyl group of the polyalkylene oxide chain of the organosiloxane-alkylene oxide copolymer into a hydroxyl group equivalent of isoheptanoic acid, isotridecanoic acid, isomyristic acid, isostearic acid, isopalmitic acid, isohexanoic acid, It can be obtained by the action of an iso-type higher fatty acid such as isoarachinic acid or isobehenic acid.

The amount of the foam stabilizer is 0.1% in the base solution (a).
It is preferable to use it in the range of 5 to 3% by weight. The reason for this is that a foam having high independent and / or open-cell properties can be obtained, and at the same time, the water absorption of the foam itself is reduced, and a sealing material having excellent water leakage prevention properties can be obtained.

In the market, as the silicone foam stabilizer of the present invention, SH-190 or SH-1 manufactured by Toray Silicone Co., Ltd.
93, etc. are L-5305 and L-5 products manufactured by Nippon Unicar.
L type such as 302, L-5350, SZ type such as SZ-1605, etc. are available, and may be used in combination as appropriate.

Examples of the fluorine-based surfactant compound include a fluoroalkylene oxide compound and a perfluoroalkylene oxide.

There are no particular restrictions on the mixing and use of the two-component polyurethane foam-type sealing material composition of the present invention, but it is preferable that each of (a) and (b) be used during the discharging and mixing operations.
The liquid is handled at a temperature of at most 130 ° C., preferably at most 90 ° C., more preferably at room temperature.

The two-component polyurethane foam-type sealing material composition of the present invention can be handled by a polyurethane molding injector (a commercially available low-pressure or high-pressure injector can be used arbitrarily). The two main ingredients are quantitatively supplied to the mixing head, and when they are mixed, they are instantaneously discharged and applied to the adherend surface of the object via the nozzle. Therefore, the mixing and discharging machine needs to have such a structure. As soon as the composition of the present invention is mixed, the (a) polyvalent mercapto compound in the base solution reacts instantaneously with the (b) component faster than the other components to form a partially crosslinked structure. Thus, it is extremely characteristic that the thixotropic effect instantaneously appears. As a result, the composition coming out of the tip of the discharge nozzle does not cause dripping at all. Thereafter, the polyol as the main component in (a) and the polyisocyanate of (b) are
When water is used as the foaming agent, the water and the isocyanate simultaneously react with each other to initiate a foaming and curing reaction, and finally, a cured product of the foamed sealing material is formed.

The two-component polyurethane foam-type sealing material composition of the present invention can be used, for example, for assembling seals of automobile window glass, for fender mirror seals of automobiles,
For automotive and vehicle body sealers, lamp sealing, signal signal sealing, refrigerator sealing, building civil engineering sealing, water-stopping materials, heat-insulating protective materials, sound-absorbing or sound-absorbing materials, in-mold foam materials, integral skin foam materials, etc. Can be used arbitrarily for a wide range of applications,
There are no particular restrictions on its use. In particular, the most suitable use is to use the composition of the present invention as a sealing material for automotive lighting and traffic lights using the composition of the present invention described below. The composition and the method of use are described below.

According to the present invention, one or both of the above-mentioned main component liquid (a) and the curing agent liquid (b) may further contain a liquid and / or crystalline plasticizer within 10% by weight, colloidal silica, One or more selected from inorganic pigments represented by calcium carbonate, carbon black, titanium white and / or pigments surface-treated with higher fatty acids thereof, at most 3 wt. Alternatively, the two-component polyurethane foam-type sealing material composition of the present invention, which is colored black and exhibits the rubber hardness of the foam of 35 or less, preferably 20 or less, for various sealing applications for vehicles,
Particularly, it is particularly preferable for lamp sealing applications in terms of suitability for recycling and heat-resistant sealing properties. In the present invention, the rubber hardness after full curing of the foam is at most 35 or less at room temperature as measured by JIS-A hardness tester, 20 or more is called a semi-rigid foam sealing material, and the case where the rubber shows a rubber hardness of 20 or less is soft foaming. It is called sealing material. The above-mentioned liquid plasticizer may be a known one, and is not particularly limited. Examples thereof include dibutyl phthalate, dioctyl phthalate, and triacetin. Similarly, examples of the crystalline plasticizer include dicyclohexyl phthalate.

As a particularly preferable use, as described above, the toned composition of the present invention is mixed and discharged in advance with a housing member for a lamp of a vehicle or the like using a urethane molding injection machine. , The composition is completely cured and cured by foaming and curing, and then integrated with an acrylic lens member or a polycarbonate lens member (the mutual members are connected with a nail pin or screw via the sealing material). Or mechanically tighten and seal with a jig such as a clip)
Light fixtures (headlamps, rear lamps or traffic lights)
Used as That is, when the two-component polyurethane foam-type sealing material composition of the present invention is used, it is possible to easily remove and contaminate the surface of the joint seal portion of each member at the time of recycling of each member of the lamp or the signal device without any contamination,
As a result, the recycled material can be effectively recycled, and the heat-resistant seal reliability of about 100 ° C. can be obtained.

The urethane prepolymer having two or more isocyanate reaction terminals which can be used as the liquid (b) in the present invention is a mixture of the polyols (I) to (XIV) with a large excess of polyisocyanate. OH of polyol
The polyisocyanate is added in such a manner that at least 2 equivalents or more of NCO groups are added to 1 equivalent of the group), so that the NCO weight% is in the range of at least 8% to 45% by weight, and the system is heated from room temperature to 130 ° C. It is preferable that the viscosity is adjusted to be 20,000 cps or less, particularly preferably 5,000 cps or less at most, as measured by a B-type rotational viscosity system. The reason is that the vapor pressure of the isocyanate can be made lower in handling than when using only the polyisocyanate alone, and the mixing workability is high.

Furthermore, there is no problem in using known storage stabilizing aids such as various organic acids and other stabilizing agents as long as they do not significantly impair the effects of the composition of the present invention. There is no. Various additives such as heat stabilizers, anti-aging agents, silane coupling agents, UV absorbers, UV stabilizers, etc. are added to one or both main agents as necessary, as long as their effects are not excluded. A small amount of an agent may be used. As the main ingredient (a), a known thixotropic agent may be used in combination with a polyvalent mercapto compound as long as the object of the present invention is not impaired. Examples thereof include monoamines having a molecular weight of 500 to 1,000 and Examples thereof include alkanolamines and aromatic or aliphatic diamines. As the product storage form of each base solution (after preparation), generally, in a state where the outside air cannot easily enter, for example, after filling in a metal round can or square can, replace with nitrogen and store in a place where direct sunlight does not shine・ Transport is essential.

[0046]

EXAMPLES Examples of the present invention are shown below together with comparative examples, but the examples do not specify or limit the present invention. In the examples, parts mean parts by weight, and% means% by weight.

Examples 1 to 5 and Comparative Examples 1 to 3 The compositions of Examples 1 to 5 and Comparative Examples 1 to 3 are as shown in Table 1, and the polyols (j) to (n) shown in Table 1 ,
Catalysts X to Y, foaming agent, foam stabilizer A to C, thixotropic agent A to
E, permanent distortion improver (α), curing agent component (b-1)
(B-4) are as follows. In Examples 1 to 5, in the case of mixing and dispersing the permanent distortion improver (α), an aqueous solution of an emulsion-type permanent distortion improver (α) having a solid content of 50% was prepared in advance, and the aqueous solution was mixed with each polyol (j). ) To (l) slowly under stirring, and then completely remove water under vacuum at 60 ° C. Then, in each of the polyols, the mixing ratio of the permanent set modifier (α) shown in Table 1 is obtained. After the addition, other components were added to prepare a base solution shown in Table 1. Polyol (j): a polyoxyalkylene-type polyether polyol, 49% of polyol EP-240 (OH value; 24 mgKOH / g, trifunctional polyether polyol) manufactured by Mitsui Toatsu Chemicals, and a thermoplastic polymer grafted type As a polyether polyol, a polymer polyol POP-34 / 2 manufactured by Mitsui Toatsu Chemicals, Inc.
8 (OH number; 28 mg KOH / g) and 1,
Mixed polyol consisting of 2% of 4-butanediol (total weight average OH value = 50.4 mg KOH / g). Polyol (k): 96% of polyol EP-3033 (OH value; 34 mgKOH / g, tetrafunctional polyether polyol) manufactured by Mitsui Toatsu Chemicals, Inc. as a polyoxyalkylene type polyether polyol, and Mitsui Toatsu Chemicals, Inc. Triol MN-400 (OH value; 420m)
gKOH / g) of 4% (total weight average OH value = 52.2 mg KOH / g).

Polyol (l): Triol MN-3050 manufactured by Mitsui Toatsu Chemicals, Inc. (OH value: 56 mg KOH) as a polyoxyalkylene type polyether polyol.
/ G, tetrafunctional polyether polyol).
15% of the following separately prepared acrylic polyol
(A OH value of the total weight average = 5)
6.5 mg KOH / g). The acrylic polyol is composed of 6 parts of methyl methacrylate and 83 parts of n-butyl acrylate.
Parts, 12 parts of hydroxyethyl acrylate, 7.64 parts of lauryl mercaptan, and 0.2 parts of azobisvaleronitrile, 500 parts of a monomer solution, 250 parts of boiling ethyl acetate 2 parts in a solvent An acrylic polyol having an OH value of 56 mgKOH / g obtained by dropping over a period of time and then polymerizing for 2 hours and removing the solvent. Polyol (m); Polymer polyol POP-34 / 45 (OH value; 43 mgKOH /
g, tetrafunctional polyether polyol) alone. Polyol (n); 10% of a polyester triol (OH value; 38 mg KOH / g) having a weight average molecular weight of about 3,000 derived from adipic acid and propylene glycol as a polyester polyol, and having a weight average molecular weight of It comprises 20 parts of an aliphatic polycarbonate diol (OH value; 54 mgKOH / g) of about 2,000 and 70 parts of EP-828 (OH value; 28 mgKOH / g) manufactured by Mitsui Toatsu Chemicals, Inc. as a polyether polyol. Mixed polyol (total weight average OH value = 3
4.2 mg KOH / g).

Catalyst (X): 30 of triethylenediamine
% Dioctyl phthalate solution (DABCO-L-1202 manufactured by Sankyo Air Products Co., Ltd.) Catalyst (Y); dibutyltin dilaurate foaming agent: distilled water foam stabilizer (a); (However, iso-PA represents an isopalmityl group.) Foam stabilizer (b); (However, iso-St represents an isostearyl group)

Thixotropic agent (A): monoaminobutane. Thixotropic agent (B); colloidal silica (Aerosil # 300 manufactured by Nippon Aerosil Co., Ltd.). Thixotropic agent (C); trimethylolpropane tris (thioglycolate). Thixotropic agent (D); pentaerythritol tetra (β
-Thiopropionate). Thixotropic agent (E); thioglycerol.

Permanent strain improver (α); vinylidene chloride resin having an average primary particle size of about 0.2 μm or less (Kurehalon latex: DO-818 manufactured by Kureha Chemical Industry Co., Ltd.)

Curing agent (b-1): As diphenylmethane diisocyanate and its polynuclear compound, 80% of MDI-PH and 20% of MDI-LK manufactured by Mitsui Toatsu Chemicals, Inc.
(NCO content = 32%). Curing agent (b-2); Crude M manufactured by Mitsui Toatsu Chemicals, Inc.
DI-CR-200. Curing agent (b-3); 5: 1 mixed diisocyanate of orthotolidine diisocyanate and tolylene diisocyanate, and polyol EP-24 manufactured by Mitsui Toatsu Chemicals, Inc.
A terminal isocyanate group (NCO is 1
8%) urethane prepolymer type curing agent. When this curing agent was used, it was heated to 45 ° C. Curing agent (b-4); EP-5 manufactured by Mitsui Toatsu Chemicals, Inc. as 1,6-naphthalenediisocyanate and polyol
05S derived from the terminal isocyanate group (NC
1: 1 mixture of urethane prepolymer (O content 9.8%) and crude MDI-CR-200 (total weight average NCO content 20.4%). When this curing agent was used, it was heated to 70 ° C.

Each composition of Examples 1 to 7 and Comparative Examples 1 to 4
Are rapidly mixed at a predetermined temperature in an aluminum cup for 2 seconds (turbine blade-shaped stirrer, rotating at 3,000 rpm), and the thixotropic onset time, cream time, foaming state, and cured state are observed. The results are shown in Table 1. In addition, at the time of curing and foaming, a test for the presence or absence of contamination on the polycarbonate transparent plate or acrylic plate was also carried out at the same time. When using a commercially available injection machine, in Examples 1 to 7, 3
The bead-shaped discharge liquid having a width of mm was observed from the time of application to the time of complete foaming and curing to prevent liquid dripping, as shown in Table 1. No problems such as mixing and ejection errors occurred.
Further, the 50% compressed state products of the foams obtained in Examples 1 to 7 were exposed at 100 ° C. for 22 hours, the compression was released, the room temperature was left to stand at room temperature, and the permanent strain rate was measured for 30 minutes as shown in Table 1. Very good. However, when a commercially available injection machine was used, the discharge was not possible in Comparative Example 3 at all, so other characteristics could not be evaluated. In Comparative Example 2, the discharge workability was good. The bead-shaped discharge liquid with a width of 3 mm on the inclined surface causes liquid dripping from the time of application to the time of complete foam hardening,
In Comparative Example 1, the liquid dripping prevention property was good, but in a pot-type foaming test, contamination with polycarbonate was observed, and the heat distortion resistance at 100 ° C. was quite poor.

In Examples 1 to 7, in all cases, regardless of the amount of the polyvalent mercapto compound added, the thixotropic imparting expression time was instantaneously (within 5 seconds) at the same time as mixing. On the other hand, in the case of the amine-based thixotropic agent, less than 0.02 gram equivalent of monoaminobutane to 100 parts
Seconds, and the flow fluidity is still observed at the beginning of the discharge. Therefore, in order to expect the effect within 2 seconds, (a) the amount of the amine-based thixotropic agent per 100 parts of the main agent should be Requires more than 0.1 gram equivalent.

Examples 8 to 11 and Comparative Examples 4 to 9 The compositions of Examples 8 to 11 and Comparative Examples 4 to 9 are as shown in Table 2, and the polyols (o) to (r) and the catalyst shown in Table 2 X to Y, a foaming agent, a foam stabilizer (d) to (e), a permanent distortion improving agent for compression or elongation (α to γ), a thixotropic agent E, a curing agent component (b-2), ( b-5) to (b-
6) means the following. Polyol (o): Polyoxyalkylene-type polyether polyol Polyol EP-240 (OH value; 24 mgKOH / g, trifunctional polyether polyol) manufactured by Mitsui Toatsu Chemicals, Inc.
Value = 24 mg KOH / g). Polyol (p): Triol MN-1000 (OH value; 170 mgKOH / g, tetrafunctional polyether polyol) manufactured by Mitsui Toatsu Chemicals Inc. alone as a polyoxyalkylene type polyether polyol. Its viscosity at 25 ° C. is 255 cps.

Polyol (q): As a polyoxyalkylene type polyether polyol, in the presence of 100 parts of Triol MN-5000 manufactured by Mitsui Toatsu Chemicals, Inc., 9
In a nitrogen stream at 5 ° C., a monomer composed of 0.25 parts of isopyropenyl-α, α′-dimethylbenzylisocyanate, 30 parts of acrylonitrile, 10 parts of styrene, and 0.55 part of benzoyl peroxide was dropped over 1 hour. The polymerization was further continued for 2 hours to obtain a polyacrylic polymer graft-modified polyether polyol (total weight average OH value = 24.1 mgKOH / g). The viscosity of the system was 46,400 cps at room temperature. Polyol (r): Prepared in a ratio consisting of 6 parts of methyl methacrylate, 85 parts of n-butyl acrylate, 10 parts of hydroxyethyl acrylate, 7.64 parts of lauryl mercaptan, and 0.2 parts of azobisvaleronitrile. 500 parts of the monomer solution thus obtained is mixed with 250 ml of boiling ethyl acetate.
Over 2 hours, then polymerized for 2 hours,
The solvent was removed to obtain an acrylic polyol. The product was an acrylic polyol having an OH value of 48 mgKOH / g and a viscosity of 7,650 cps at 30 ° C.

Catalyst (X): 30 of triethylenediamine
% Dioctyl phthalate solution (DABCO-L-1202 manufactured by Sankyo Air Products Co., Ltd.) Catalyst (Y); dibutyltin dilaurate foaming agent: distilled water foam stabilizer (d); (However, iso-St represents an isostearyl group.) Foam stabilizer (e); SH-200, a product of Toray Silicon Co., Ltd.

Permanent strain improver (α); vinylidene chloride resin having an average primary particle size of about 0.2 μm (using Klehalon latex: DO-818 manufactured by Kureha Chemical Industry) Permanent strain improver (β) An average primary particle size of about 0.15;
Resin containing 50% of micron vinyl chloride-dioctyl phthalate (vinyl chloride; average molecular weight 35,000) Permanent set modifier (γ); average particle size of primary particles is about 0.10
Micron vinylidene fluoride resin (vinylidene fluoride;
(Average molecular weight: 58,000) Thixotropic agent (E); thioglycerol. Curing agent (b-2); Crude M manufactured by Mitsui Toatsu Chemicals, Inc.
DI-CR-200. Curing agent (b-5); terminal isocyanate group (NCO content) derived from 5: 1 mixed diisocyanate of tolidine diisocyanate and tolylene diisocyanate, and polyol EP-240 and Aerosil # 300 manufactured by Mitsui Toatsu Chemicals, Inc. (2.4%) a urethane prepolymer type curing agent having a viscosity of 22,000 cps at 120 ° C. Curing agent (b-7): A urethane prepolymer-type curing agent (NCO content: 11) using a large excess of MDI-LK as diphenylmethane diisocyanate and a terminal isocyanate group from EP-828 of polyether polyol.
%) Was prepared.

Examples 8 to 11 and Comparative Examples 4 to 11 shown in Table 2
Table 3 shows the viscosities and handling temperatures of each of the base solution and the hardener solution of No. 9. Fill each of the two nitrogen-replaced normal pressure tanks with the main agent and the curing agent, and set them to a tilt angle of 45 ° at the temperature shown in Table 3 with a commercially available plunger pump interlocking drive type, continuous, mixed discharge injection machine. 5 mm in width and continuously discharged horizontally for 10 to 30 seconds. The time lag from the mixing head to the nozzle tip passes within 2 seconds. As shown in Table 2, the results of the mixed foaming test of each composition in Table 2 showed the relationship between the mixing ratio and working stability (ejection stability of foam physical properties) in Examples 8 and 9 as shown in Table 2. In the discharge test, the physical properties of the foam over time are quite stable,
Workability was good. In Examples 8 and 10, the influence of the amount of the catalyst was observed, but it was confirmed that these were preferable action hardening regions. Example 11 is a case where the amount of the aqueous foaming agent in the base solution was 1%. However, the preferable urethane foaming agent of the present invention was obtained without any problem. In Comparative Examples 4 to 9, the composition does not become a foam without the addition of the tertiary amine, and the effect of the thixotropic agent is not exhibited (Comparative Example 5). The rise time is extremely short, the workability is lacking, the cell is rough or the problem is severe (Comparative Example 4), and the amount of the curing agent is 当 equivalent to 1 equivalent of active hydrogen of the main agent. In this case, the heat resistance of the foam is insufficient (Comparative Example 7), and when the amount of the catalyst used is small, the curing time is extremely long, and disadvantages such as remarkable curing shrinkage and insufficient heat resistance rigidity are exhibited (Comparative Example 6). Etc. became clear. In Comparative Examples 8 and 9, workability was examined when the viscosities of the main agent and the curing agent exceeded 20,000, but it was found that no ejection stability was obtained.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

Example 12 To 100 parts of the main ingredient (a) of the composition shown in Example 1 in Table 1, 5 parts of dicyclohexyl phthalate, 0.1 part of carbon black, and titanium white (MR-
930) were added 10.1 parts of a gray pigment consisting of 5 parts, and the mixture was heated and mixed at 45 ° C., and the main agent toned in gray and the curing agent (b-3) were also heated at 45 ° C. While maintaining the state, the main agent tank and the hardening agent tank are put into each of two nitrogen-replaced normal pressure tanks, and the main agent 1 is supplied by a commercially available plunger pump interlocking drive type continuous / mixing discharge injection machine.
At a mixing / discharging temperature of 45 ° C., a U-shaped seal forming portion having a width of 5 mm and a height of 10 mm of a polypropylene housing member was added so that the mixing ratio of the curing agent was 36.9 parts with respect to 00 parts. The composition was mixed and discharged, and the width was 5 mm and the height was 1
A foam was formed at 0 mm. Cured at room temperature until the next day, (the rubber hardness (JIS-A) at that time was 10 to 11). The transparent polycarbonate lens member was clipped to each other with clips so that the foam at the sealing site was compressed by 50%. Concluded. A state where the temperature of the sealed portion is heated to 80 to 90 ° C. for a long time (1 hour) → shower ring (5 minutes) → transverse vibration load of 500 Hz per minute at room temperature 5 minutes) → Return to the initial test, 100
No water leaked into the lamp during the cycle test. After the test, the clip was removed, and the lens material was recovered without any fogging or contamination of the sealing material. The same was true for the housing member.

[0064]

Industrial Applicability The two-component polyurethane foam-type sealing material composition of the present invention has excellent workability with a mixing and injection machine,
In addition, the liquid dripping prevention property is sufficiently exhibited, and the sealing material can be favorably formed even on an inclined surface. Also, when used in a high-temperature environment of 100 ° C., it is extremely resistant to distortion. Moreover, it can be used as a substitute for a glass material without any influence on a lightweight and transparent engineering resin such as polycarbonate or acrylic resin. Therefore, it is excellent as a foam sealing material for recyclable vehicle lamps such as automobiles.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-49-31800 (JP, A) JP-A-51-77694 (JP, A) JP-A-54-118498 (JP, A) JP-A-62 232480 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 75/04-75/12 C08G 18/00-18/87 C09K 3/10

Claims (10)

(57) [Claims] (1) a total weight average hydroxyl value is 10 to 1;
For 100 parts by weight of polyol in the range of 50 mgKOH / g, 0.0001 to 3 parts by weight of a catalyst as an additive,
O. of water blowing agent A base liquid (a) containing 1 to 1 part by weight, 0.1 to 3 parts by weight of a foam stabilizer, and 1 to 50 parts by weight of a permanent set modifier for compression or elongation, and a polyisocyanate and / or at least 2 parts by weight. A curing agent liquid (b) comprising a modified polyisocyanate having at least two terminal isocyanate groups is added to 100 parts by weight of (a) and 1 part of (b)
In a two-component polyurethane foam-type sealing material composition which is mixed and used so as to have a mixing ratio of 0 to 300 parts by weight, a permanent distortion improving agent for compression or elongation in the base material liquid (a) contains a polymer primary particle. A two-component polyurethane foam-type sealing material composition characterized in that it is a halogen-based thermoplastic resin having an average diameter of at most 2 microns at most. 2. A total weight average hydroxyl value of 10 to 1
For 100 parts by weight of polyol in the range of 50 mgKOH / g, 0.0001 to 3 parts by weight of a catalyst as an additive,
O. of water blowing agent 1 to 1 part by weight, 0.1 to 3 parts by weight of a foam stabilizer, 1 to 50 parts by weight of a permanent set modifier for compression or elongation, and 0.001 to 0.20 gram equivalent of a thixotropic agent. And a curing agent liquid (b) comprising a polyisocyanate and / or a modified polyisocyanate having at least two terminal isocyanate groups, based on 100 parts by weight of (a) Of 1
In a two-component polyurethane foam-type sealing material composition which is mixed and used so as to have a mixing ratio of 0 to 300 parts by weight, a permanent distortion improving agent for compression or elongation in the base material liquid (a) contains a polymer primary particle. A two-component polyurethane foam-type sealing material composition, which is a chlorine-based thermoplastic resin having an average diameter of 2 μm or less at most, and wherein a thixotropic agent contains a polyvalent mercapto compound. 3. The two-component polyurethane according to claim 1, wherein the halogen-based thermoplastic resin is one selected from a vinylidene chloride resin, a vinylidene fluoride resin, a vinyl chloride resin, and a vinyl fluoride resin. Foam-type sealing material composition. 4. The two-component polyurethane foam-type sealing material composition according to claim 3, wherein the addition amount of the halogen-based thermoplastic resin is in the range of 1 to 15% by weight in the base liquid (a). object. 5. The polyvalent mercapto compound as a thixotropic agent is a compound selected from aliphatic mercaptoglycerols, aliphatic dimercapto compounds, aliphatic trimercapto compounds, aliphatic tetramercapto compounds and mixtures thereof. 3. The two-component polyurethane foam-type sealing material composition according to claim 2, wherein at least 0.005 to 0.20 g equivalent is contained per 100 parts by weight of the base liquid (a). 6. The polyol comprises one or more of the following (A) to (C), and the total weight average hydroxyl value of the polyol is 20 to 80 mg KOH.
/ G. The two-component polyurethane foam-type sealing material composition according to claim 1 or 2. (A) Polyether polyols (B) Polymer polyols (C) Polyester polyols 7. A mixture obtained by mixing one or both of the main agent liquid (a) and the curing agent liquid (b) according to claim 1 with a mixing and discharging machine onto a member, and after foaming and curing, the other A method of sealing between members, characterized by being integrated with the member. 8. A mixture obtained by mixing one or both of the base liquid (a) and the hardener liquid (b) according to claim 2 with a mixing / discharging machine, discharging the mixture onto a member, foaming and curing, and then adding A method of sealing between members, characterized by being integrated with the member. 9. A mixture obtained by mixing one or both of the base liquid (a) and the hardener liquid (b) according to claim 1 with a mixing / discharging machine is discharged onto a lamp housing member and foamed and cured. Later, a lamp obtained by integrating with a lens member made of resin. 10. A mixture obtained by mixing one or both of the main agent liquid (a) and the curing agent liquid (b) according to claim 2 by a mixing and discharging machine is discharged onto a lamp housing member and foamed and cured. Later, a lamp obtained by integrating with a lens member made of resin.