JPH01278559A - Urethane-based one-pack moisture-curable composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in adhesivity even without the need for primer and in long-term stability in its adhesiveness, suitable for the adhesives, sealers etc. between automobile body and glazing by incorporating primary components with a specified amount of specific plasticizer. CONSTITUTION:The objective composition can be obtained by incorporating (A) priminary components; i.e., a polyol (e.g., polytetramethylene glycol) and a polyisocyanate (e.g., tolylenediisocyanate) with (B) as a plasticizer, 5-20wt.% of a phthalic acid compound of formula I (n is >=10) and/or a trimellitic acid compound of formula II (m is >=8. Preferably, the compound of the formula I is diundecyl phthalate or diisodecyl phthalate, while the compound of the formula II tri-(2-ethylhexyl)trimellitate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a urethane-based one-component moisture-curing composition used as an adhesive or a sealant used for bonding an automobile body to a car door, and in particular, The present invention relates to a composition that exhibits excellent adhesion even without a brimer.

<Prior art and its problems> Hitherto, urethane-based one-component sealing materials that utilize moisture curing have been proposed; for example, Japanese Patent Publication No. 51-38735
The publication discloses a prepolymer consisting of a mixed polyol of 1 mole of triol (average molecular weight: 34,500) and 5 moles of diol (average molecular weight: 2,000) and diphenylmethane-4,47-diisocyanate.

However, such one-component urethane-based moisture-curable compositions have the disadvantage of poor adhesion when used without a primer (frymer) on a coated board, and the substrate surface (coated board) in contact with it is coated with a primer. It is common practice to apply a urethane composition after a coating treatment.

This brimer not only improves compatibility with the coated plate as mentioned above, but also has the effect of forming a barrier layer to prevent water, plasticizers, etc. from the urethane composition from migrating to the coated plate and deteriorating the coated plate. I also have

In recent years, there has been a demand for urethane compositions to be used in a wider range of applications and to improve workability, and urethane compositions that can be used without brimer treatment have been developed.

However, if a brimer is not used, the plasticizer in the composition will migrate to the coated plate over time, causing problems such as peeling between the coated plate and the composition.

<Invention or Problems to be Solved> The purpose of the present invention is to solve the problems of the prior art and to provide a one-component urethane-based moisture-curable composition that has excellent adhesive properties over time even without a brimer. , try.

<Means for Solving the Problems> The present invention is characterized in that the main component is a urethane prepolymer consisting of a polyol and polyisocyanate-1, and has the following formula [A] and/or [B] as a plasticizer. Provided is a one-component urethane-based moisture-curable composition.

(Here, n is an integer of 10 or more) (Here, m is an integer on BJJ) Here, 5 to 20 wt. % is preferable.

Dismissed, a detailed explanation of the tree invention.

The composition of the Wood invention contains a phthalic acid compound represented by the following formula [A] and/or a trimellitic acid compound represented by the following formula [B] as a plasticizer.

○]] (Here, n is an integer of 10 or more) 1))] (Here, m is an integer of 8 or more) A phthalic acid compound represented by formula [A] where n is 10 or more has a composition It improves the adhesion of the composition of the wood invention since it makes the material soft and there is less migration to the coated board.

Examples of the phthalic acid compound represented by the formula [A] include diisodecyl phthalate (DIDP) and syl-1-lidecyl phthalate (DTDP).

Preferred examples include cyundecyl phthalate (DUP) and sibdelphthalate (DIPP).

The trimellitic acid compound represented by the formula [B] with m=8 or more makes the composition soft, has less transferability to the coated plate, and improves the adhesiveness of the composition of the present invention.

As the l-limellid I-acid compound represented by formula [B], tri(2-ethylhexyl)+-limellid-h(
TOTM), 1~Liisoocdyltrimerite-1・(T
IOTM), triisodecyltrimerite-1-(T
IDTM).

Preferably, Tory (2-ethylhexyllimerite 1)
-(TOTM) is good.

The amount of [A] and/or [B] used as a plasticizer is preferably 5 to 20 wL% based on the entire composition.

If the plasticizer content is less than 5%, the hardness will be too high, making it unsuitable as a sealant, and if it exceeds 20%, there will be problems in that it will have a negative effect on adhesion and the hardness will be too low.

The main component of the composition of the present invention is not particularly limited, and may be any component commonly used in one-component urethane moisture-curable compositions.

Any urethane prepolymer consisting of a polyol and a polyisocyanate as a main component may be used.

Polyols used in wood invention include polyether polyols such as ramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol, and olefin polyols such as polybutadiene polyol and polyisoprene polyol. Polyester polyols such as polyols, adipate polyols, rough monopolyols, and castor oil can be used.

Considering water resistance and weather resistance, polyether-based and polyolefin-based polyols are preferred.

In addition, polyisocyanates that can be combined with several types of these polyols as required include l-lylene isocyanate-1.
・, diphenylmethane 4.4' -cyisocyanate-1-
Also, modified products thereof such as 1,5-naphdylene diisocyanate, bitlylene diisocyanate, and lylene diisocyanate may not be used.

The moisture-curable urethane prepolymer uses moisture in the air or other sources as a curing agent, and diphenylmethane-4,4' diisocyanate-1- is preferred from the viewpoint of reactivity and cost.

The catalyst used is not particularly limited or is usually used for urethane (
1 Known as gold R (tin, lead, potassium, titanium, bismuth, nickel, cobalt, iron, calcium, magnesium, cadmium, mercury, etc.), salt, amine catalyst (-tertiary amine for boat fishing) ), acidic catalysts such as carboxylic acids can be used.

The composition of the present invention includes a urethane prepolymer composition containing an inert filler, a plasticizer, a solvent, a catalyst for accelerating curing, etc. with respect to incyanate groups in order to impart desired physical properties to the composition. They may be mixed.

Fillers include carbon black, clay, talc,
Calcium carbonate or a mixture thereof may be used.As a plasticizer, in addition to the above-mentioned plasticizers, phthalate conductors such as sibdelphthalate or sibdelphthalate may be used, and tetrahydrophthalate may be used as the plasticizer, without changing the gist of the invention. Examples of solvents in which conductors such as acids, azelaic acid, maleic acid, trimellitic acid, isophthalic acid, adipic acid, itaconic acid, and citric acid can be used include aromatic hydrocarbons such as toluene and xylene. Ru.

The urethane-based one-component moisture-curable composition of the tree invention preferably uses a curing catalyst described below for the urethane polymer as the main component, or a curing catalyst described below is further added to the curing catalyst. Compositions that use adhesion promoters have strong adhesion to coated plates, and there is no deterioration in adhesion over time.

Preferably, the curing catalyst is tin-based 11! l! A mixed catalyst consisting of an amine catalyst and an amine catalyst is used.

Examples of the tin-based catalyst include stannath octoate, sibdeltin dilaurate, silver dioctylate silaure-1., and sibdeltin acetate-1.

Dioctyltin dilaurate is preferred.

Examples of amine catalysts include monoamines, cyamines, triamines, and cyclic amines.

Morpoline-based amines are good for this purpose.

The combination of the tin-based catalyst and the amine-based catalyst is preferably dioctyltin dilaurate or morpoline-based amine.

The mixing ratio of the amine catalyst to the tin catalyst is 1 by weight.
/1 to 1/10 is preferred. This is because within this range, the adhesion to the painted surface is good even without the use of a brimer.

The amount of the mixed catalyst of the tin-based catalyst and the amine-based catalyst to be used is preferably 01 to 10 phr (parts by weight relative to 100 parts by weight of the main material).

As an adhesion promoter, a polyalkylene ether diol with an average molecular weight of m400 to 2000 and an excess of aliphatic and/or
Alternatively, a urethane prepolymer made of alicyclic isocyanate is used.

Such adhesion promoters are believed to contribute to adhesion by increasing the concentration of incyanate groups in the composition.

As a polyalkylene ether diol, Bolite) ~
Examples include ramedylene glycol, polyethylene glycol, and polypropylene glycol.

P completed, Volite [・Ramethylene glycol is good.

Examples of the aliphatic isocyanes include hexane methylene isocyanes-1 and the like.

Examples of the alicyclic incyanate include inholodiisocyanate, hydrogenated diphenylmethane-4-4'-cyisocyanate-1.(hydrogenated MDI), and preferably hydrogenated MDI.

The amount of the adhesion promoter described in item 1 to be added is preferably 2 to 15 phr based on the base agent.

If it is less than 2 phr, adhesion promoting effect will be seen, 15 phr
When the temperature exceeds 100%, foaming becomes more likely in high temperature and high humidity conditions and in high temperature water.

The method for producing the composition of the present invention is not particularly limited, but preferably, the base material, adhesion promoter, plasticizer, filler, and other additives are thoroughly kneaded under reduced pressure, and each component is uniformly dispersed. Alternatively, the curing catalyst may be dissolved in a solvent such as xylene, and then thoroughly kneaded under reduced pressure to form a composition.

<Examples> The present invention will be specifically explained below using Examples, but the present invention is not limited thereto.

(Example 1 and Comparative Example 1.2) 57 parts by weight of polyoxypropylene triol having an average molecule '# of 5000 having 3 hydroxyl groups and 23 parts by weight polyoxypropylene ether thiol having an average molecule [2000] having 2 hydroxyl groups was placed in a reaction vessel and heated at 110°C for 50 m
After dehydrating under reduced pressure at m Hg for 2 hours, it was cooled to 80°C.
To this, 9.1 parts by weight of a mixture of 24-tolylene diisocyanate-1 and 26-tolylene diisocyanate (8020) was added without stirring, and the free isocyanate was reduced to 22%.
The reaction was carried out until the TDI prepolymer (urethane prepolymer (X)) was obtained.

At the same time, 1 to 196 parts by weight of diphenylmethane-4,4'-cyisocyanate were added to this TDI prepolymer and stirred, and 85 parts by weight of polypropylene triol having an average molecular weight of 5000 and an average molecular weight of z2ooo, which had been previously dehydrated, were added.
35 parts by weight of boriflohylene ether siol was added and reacted at 80° C. until free incyanate was reduced to 18% to obtain an MDI prepolymer (urethane prepolymer (Y)) to obtain a urethane prepolymer composition. Ta.

100 parts by weight of this prepolymer was placed in a gauze mixing machine container containing dried nitrogen scum, and 20 parts by weight of dehydrated plasticizer was added.
100 parts by weight of dry carbon black and 10 parts by weight of dry calcium carbonate were added and thoroughly kneaded under reduced pressure.

After each component was uniformly dispersed, a catalyst was added, which was a mixture of dehydrated xylene, Shidikudylartin Silaure 1~ (DOTL), and N,N' Shimedylaminoethylmorpholine (DABCOX-DM) in the weight ratio shown in Table 1. Then, sufficient kneading was performed under reduced pressure to obtain a composition.

This composition was adhered using coated plate A shown in Table 2 without a brimer, and the adhesive strength was evaluated by the following method.

(1) Adhesion evaluation test (adhesiveness before hand 71) Preparation method of test piece The composition was applied in the shape of a bead on release paper, and the temperature was 35±
After 5 minutes at 2℃ and 95±5%RH, invert onto the coated plate.
Crimp to mm thickness.

Initial aging condition of test piece: The test piece was left at 20°C and 65% RH for 7 days.

Hot water resistance: The test specimen was left at 20°C and 65% RH for 7 days, and then immersed in 40°C hot water for 30.60 days.

For the test piece prepared as above, 2 cm from the edge of the coated plate
Use a knife to peel off the adhesive from the part, and remove it from the board surface.
Adhesion was tested by pulling in the direction of an angle of 0° or more (approximately 150°). At this time, the knife was placed in contact with the adhesive at an angle of 60° with respect to the plate surface.

Table 1 Note 1) DMP Shimedil Phthale-1, 2) DOP Shibdel Fumarate 3) DIDP Shibdel Fumarate-4) TB TM ), Libdel 1-Limeritate-1, 5) To TM Triocdyl Trimeritate 6) DOA 1.7) DODA di(n-octyl, n-decyl)adipate 8) DBS dibdel sebacate 9) DOS 1.1 0) DBM di(n-octyl, n-decyl) adipate +1. ) DOM dioctyl maleate 12) DBF sibdel fumarate + 3) DOF sibdel male-1 + 4) TBP tributyl physphate 15) TOP trioctyl physphate 1 - Table 2 <Effects of the invention> The composition of the present invention has a specific Since the plasticizer is used, the deterioration of the coated plate due to the plasticizer can be minimized, and the adhesion to the coated plate is improved when no brimer is used, resulting in excellent long-term adhesive stability.

Same dialect 1 ri →・ stone zu 1゛V′easy −
・-]・1, -1 1---Shi count thread sales adjustment (pulling method) % formula % 2. Name of the invention Urethane one-component moisture curing type Afl composition 3 Amendment person case and Relationship Patent applicant name Name Yokohama Rubber Co., Ltd. 4 agent Address: 101 Telephone 864-4498
3-2-2 Iwamoto-cho, Chiyoda-ku, Tokyo July 26, 1988 (Delivery) 6 Column 7 for “Title of the Invention” in the application and specification to be amended Contents of the amendment (1) Please copy the application on a separate sheet. Correct as expected.

(2) "Urethane-based one-component moisture-curable composition (2)" in line 3 of page 1 of the specification is corrected to "urethane-based one-component moisture-curable composition."

Claims (2)

[Claims] (1) The main component is a urethane prepolymer consisting of polyol and polyisocyanate, and the following formula [A
] and/or [B] A one-component urethane moisture-curable composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[A] (Here, n is an integer of 10 or more) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[B] (Here, m is an integer of 8 or more. be) (2) The urethane-based one-component moisture-curable composition according to claim 1, wherein the following formula [A] and/or [B] is 5 to 20 wt% based on the entire composition.