JPH02167365A - Thixotropic polyurethane resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having thixotropic properties imparted thereto, excellent in storage stability and suitable as coating materials, adhesives, etc., by blending a polyurethane resin with hydrophobic colloidal silica and bisalkoxysilyl compound. CONSTITUTION:A resin composition obtained by blending (A) 100 pts.wt. polyurethane resin with (B) 0.5-50 pts.wt. hydrophobic colloidal silica and (C) 0.1-30 pts.wt. bisalkoxylsilyl compound expressed by the formula (R is O or 1-15C alkylene bridge; R<1> and R<2> are CH3, C2H5, etc.; m is 1-4; n is 2 or 3).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyurethane resin product used as a coating material, adhesive or sealing material, particularly)
The present invention relates to a polyurethane resin composition that has been given g-modification.

[Conventional technology]

When polyurethane resin is used as a coating material, adhesive, or sealant, it is necessary to impart species modification to the resin because it is applied on a vertical or sloped surface.

As a method for imparting species modification to polyurethane resin,
A number of proposals have already been proposed.

For example, in Japanese Patent Publication No. 45-41110, a species-modified polyurethane resin consisting of a combination of colloidal silica and a polyoxyethylene glycol derivative, and in Japanese Patent Publication No. 47-76'32, a non-aluminous filler such as colloidal silica is used. and a polyoxyalkylene compound;
Japanese Patent Publication No. 1983-80354.51-47
No. 046.60-108479,6 (1-120750) proposes a species-modified polyurethane resin composition.

However, all of these tg-modified polyurethane resins use hydrophilic colloidal silica as the main ingredient of the temperature imparting agent.

(Problem to be solved by the invention) The storage stability of polyurethane resin in a closed container is
This is an important performance in this type of coating material, adhesive, or sealant, and its quality determines the commercial value in the market.

It goes without saying that the 111M product is preferable because it has high storage stability in a closed container at a temperature relatively higher than room temperature, that is, 50° C., and has little change in workability.

[Means for solving the problem] The use of hydrophobic colloidal silica has the following advantages compared to hydrophilic colloidal silica:
It is known that storage stability is improved. However, although the use of this type of silica has the effect of thickening the resin composition, the species modification is insufficient.

Therefore, the present inventors investigated compositions that should be combined with hydrophobic colloidal silica in order to impart Ti modification, and found that conventional polyoxyethylene derivatives, dimethyl sulfoxide, tetramethylurea, etc. polar solvents, etc.
It was found that conventionally known combinations were unable to impart coal extractability, and as a result of further intensive research, it was discovered that bisalkoxysilyl compounds were extremely effective in imparting species modification, and the present invention was finally achieved.

That is, the present invention provides the following general formula, (CH)3-n (R'○)n-3i -R-31-(OR2)n ・
...(CHs)gon (wherein, R represents an oxygen atom or an alkylene bridge having 1 to 15 carbon atoms, and this alkylene bridge may be linear or branched, or may not contain a heteroatom. It's okay to stay.

R' and R2 are CH, or C2H5 or CmHzm
++0CZH4 or CmH2m+, ○ c 2H, ○ C, H,, m is 1
~4, indicating n=2 or 3. ) The present invention relates to a thixotropic polyurethane resin composition containing a bisalkoxysilyl compound represented by:

That is, the present invention is a corner-modified polyurethane resin composition containing a polyurethane resin, hydrophobic colloidal silica, and the bisalkoxysilyl compound.

The polyurethane resin, which is the first component of the present invention, is an isocyanate-terminated prepolymer obtained by reacting a polyisocyanate with a known compound having two or more active hydrogens in one molecule in an excess of isocyanate. Or it is a mixture of the isocyanate-terminated prepolymer and a latent active hydrogen compound.

The polyisosoatom-1, which is a component of the polyurethane resin of the present invention, is 1)) lylene diisocyanate (including various mixtures of isomers), diphenylmethane diisocyanate (including various mixtures of isomers), 3.3゛-dimethyl-4,4-
Biphenylene diisocyanate, R-to 1 4-phenylene diisocyanate, xylylene diisocyanate, tetramenalxylylene diisocyanate, naphthylene diisocyanate, dicyclohexylmethane-4,4-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenation xylylene diisocyanate, 1,4-cyclohexyl diisocyanate,
Diisocyanates such as 1-methyl-2,4-diisocyanato-cyclohexane, 2,4,4-trimethylto-6-diisocyanatohexane, 2) 4,4"-4°-triphenylmethane triisocyanate, tris( Triisocyanates such as 4-phenylisocyanato) thiophosphate, 3) Urethane-modified products, isocyanurate-modified products, carbodiimide-modified products, biuret-modified products of the above isocyanates, crude tolylene diisocyanate, polymethylene poly It is a polyfunctional isocyanate such as phenyl isocyanate.

The prepolymer having an isocyanate group as a terminal group used in the present invention is a prepolymer having two or more active hydrogen atoms in one molecule, such as the above-mentioned various organic polyisocyanate compounds, known polyols, and known polyamines. The compound is reacted with a compound by a known method so that free isocyanate groups remain.

That is, it is produced by reacting an isocyanate and a known compound having active hydrogen in a loo'c for several hours.

Its isocyanate group content is 0.5-1000% by weight
is preferred.

The known compounds having two or more active hydrogens in one molecule used herein are those having two or more hydroxyl groups, one or more amine groups, two or more mercapto groups, or Examples include compounds having a hydroxyl group and an amino group, or compounds having a hydroxyl group and a mercapto group.

Examples of such compounds include water, polyhydric alcohols such as ethylene glycol, propylene glycol, chrycerin, trimethylolpropane, pentaerythritol, sorbitol, and LJ sugar; , aromatic amines such as ethylene cyanide, ethanolamine, etc.
Propylene oxide or propylene oxide and ethylene oxide are added to an aliphatic amine or alkanolamine such as jetanolamine, a compound having two or more active hydrogens in one molecule, or a mixture of these compounds, and polymerized by addition polymerization. Polyether polyols, polyether polyols obtained by converting the hydroxyl groups of the polyether polyols to amino groups, polytetraethylene ether polyols,
Polycarbonate polyols, polycaprolactone polyols, polyester polyols such as polyethylene adipate, polybutadiene polyols, esters of higher fatty acids such as castor oil, polyether polyols, or polyester polyols obtained by grafting vinyl monomers. These include polymer polyols, compounds obtained by copolymerizing known ethylenically unsaturated monomers having one or more active hydrogens in one molecule, and ethers having a mercapto group.

The latent active hydrogen compound used in the polyurethane resin, which is the first component of the present invention, is a compound whose active hydrogen is regenerated by moisture.

Latent active hydrogen compounds whose active hydrogen is regenerated by moisture include polyketimine shown in British Patent No. 1064841, polyenamine shown in Japanese Patent Publication No. 5716126, and Japanese Patent Publication No. 62. -01
β-amino-β-lactam shown in 1233,
Further, there are compounds such as oxazolidine.

The mixing ratio of the isocyanate-terminated prepolymer and the latent active hydrogen compound is such that the ratio (equivalence ratio) between the number of isocyanate groups and the number of active hydrogens generated during hydrolysis is:
0.7 to 1.3 is preferred.

The polyurethane resin that is the first component of the present invention has a viscosity,
Fillers, plasticizers, solvents, adhesion promoters, colorants, and stabilizers can be mixed to adjust the physical properties and resistance of the resin.

Examples of fillers include calcium carbonate, talc, kaolin, zeolite, diatomaceous earth, vinyl chloride paste resin, glass balloons, vinylidene chloride resin balloons, etc.
Used in resins at a maximum of 60% by weight.

Plasticizers include, for example, dioctyl phthalate, dibutyl phthalate, dilauryl phthalate, butylbenzyl phthalate, dioctyl phthalate, diisodecyl adipate, trioctyl phosphate, etc.
Solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, and octane, petroleum solvents ranging from gasoline to kerosene fractions, and acetic acid. These include esters such as ethyl and butyl acetate, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ether esters such as cellosolve acetate and butyl cellosolve acetate, and are used in resins at a maximum of 50% by weight.

Silane camplar or the like is used as an adhesion promoter, carbon blank, titanium white or the like is used as a coloring agent, and a hindered phenol compound, a triazole compound or the like is used as a stabilizer.

The third component of the present invention, hydrophobic colloidal silica, is
It is obtained by reacting hydrophilic colloidal silica obtained by combustion hydrolysis with dimethyldichlorosilane or trimethylchlorosilane to make the surface hydrophobic.

AERO3IL R972 (DEGUSSA), W
ACKER HDK H-20 (WACKER) and the like are typical hydrophobic +'L colloidal silicas.

The bisalkoxysilyl compound, which is the third component of the present invention, is: 1) 1.6-bis(trismethoxyethoxyethoxysilyl)hexane, 1.2-bis(trimethoxysilyl)
Ethane, bis[3-()ethoxysilyl)propylcotetrasulfide, bis[3-(triethoxysilyl)
bisalkoxysilyl compounds such as propyl]anξane and 13-dimethyltetramethoxydisiloxane; 2) bisalkoxysilyl compounds obtained by reaction between alkoxysilyl compounds (compounds generally called silane coupling agents); For example, 1 mole of isocyanate propyltriethoxine and 1 mole of N-
Compound obtained by reaction with butyl-T-agonopropyltrismethoxyshethoxysilane, compound obtained by reaction of 1 mol of isocyanatepropyltriethoxysilane with 1 mol of mercaptoethyltriethoxysilane, 1 mol The compound obtained by the reaction of isocyanate probyltrismethoxyethoxysilane with 1 mol of hydroxyethyltriethoxysilane, 1 mol of γ
- Compound obtained from the reaction of aminopropyltrismethoxyethoxysolane and 1 mole of T-glycidoxypropyltrismethoxyethoxysilane, 3) Compound obtained from the reaction of 2 moles of a monosilane compound having active hydrogen and 11 moles of diisocyanosilane. For example, compounds obtained by the reaction of T-antanoprobyl trismethoxyethoxyethoxysilane and isophorone diisocyanate, mercaptoethyltriethoxysilane and diphenylmethane diisocyanate, hydroxyethyltriethoxysilane and xylylene diisocyanate, and the like.

The mixing ratio of the composition of the present invention is 100% polyurethane resin.
Based on parts by weight, hydrophobic colloidal silica is 0.5 to 5
0 parts by weight, bisalkoxysilyl compound 0.1-30
Parts by weight are particularly preferred.

In the present invention, the polyurethane resin composition containing hydrophobic colloidal silica and the bisalkoxysilyl compound has high storage stability, and can yield a resin with little change in workability even at relatively high temperatures.

(Examples) Hereinafter, in order to explain the present invention more specifically, Examples and comparative examples will be given and explained, but the present invention is not limited to these Examples.

In addition, the middle part of the example indicates parts by weight.

The following raw materials were used in the examples.

Isocyanate "'°" Preboimer: Prepolymer A... As the diisocyanate, 598 parts of 2.4-1 lylene diisocyanate, 2600 parts of polyoxypropylene glycol (molecular weight 2000), Propylene triol (molecule Eit3000)
Prepolymer A was obtained by reacting with 1802 parts at 100°C for 10 hours.

Terminal NGO group is 1.89%, viscosity is 41,0OOcps
/25°C.

Prepolymer B: 1973 parts of isophorone diisocyanate was used as the diisocyanate, 5081 parts of boroxypropylene glycol (molecule 13000),
Polyoxypropylene triol (15000 molecules)
Prepolymer B was obtained by reacting 3946 parts and 0.5 parts of dibutyltin dilaurate as a catalyst at 100'C for 3 hours.

Terminal NGO group is 1.12%, viscosity is 4B, 0OOcps
/25°C.

Prepolymer C... As diisocyanate, p,
Using 218 parts of p'-diphenylmethane diisocyanate, polyoxypropylene glycol (130 parts by molecule)
00) 1185 parts, 397 parts of polyoxypropylene triol (molecule 14000), and 0.02 parts of dibutyltin dilaurate catalyst were reacted at 100°C for 5 hours,
Next, 200 parts of xylene was charged while cooling in air to obtain Prepolymer C.

Terminal NGO group is 1.31%, viscosity is 17.200 cps
/25°C.

Hydrophobic colloidal silica: WACKERHDK H-20 Latent active hydrogen compound: Enamine: For producing enamine (ENA) obtained by condensing a secondary amine with an aldehyde or ketone. Examples of combinations suitable for the present invention are as follows.

That is, ENA-1 is obtained by condensing 1 mole of dimer tall oil fatty acid and 2 moles of anhydrous piperazine, and then condensing 1 mole of the obtained secondary shea fruit with 2 moles of 3.3゜5-trimethylcyclohexanone. This is the enamine obtained by

β-Ano β-lactam: A combination suitable for the present invention when producing β-amino-β-lactam (LAC) by adding an organic isocyanate to a condensate of a secondary amine and an aldehyde. An example is as follows.

That is, LAC-1 is 4.4”-dipiperidylpropane 1
After condensing 2 moles of isobutyraldehyde to mol,
It is a lactam obtained by adding 2 moles of o-1-lyl isocyanate.

Bisalkoxysilyl compound: Bisalkoxysilyl compound A... 245 parts of isocyanatepropyltriethoxysilane, N-butyl-γ-
499 parts of aminopropyltrismethoxyethoxyethoxysilane was added dropwise with stirring, and after the addition was completed, the temperature was 60°C.
′? After reacting for 1'1 hour, bisalkoxysilyl compound A (BSA) was obtained.

Bisalkoxysilyl compound B: 443 parts of γ-aminopropyltrismethoxyethoxyethoxysilane was added dropwise to 112 parts of isophorone diisocyanate with stirring, and after the addition was completed, the reaction was carried out at 60'C'r for 1 hour to form bisalkoxysilyl compound B. (BSB) was obtained.

Bisalkoxysilyl compound C...208 parts of hydroxyethyltriethoxysilane was added dropwise to 87 parts of tolylene diisocyanate with stirring, and after the addition was completed, the temperature was 80°.
C for 5 hours to form a bisalkoxysilyl compound C.
(BSC) was obtained.

Species degeneration was evaluated by the slump test specified in 6.2 of JIS-A575B (1986).

Changes in storage stability and workability were evaluated as a liquid temperature air-curable polyurethane resin composition, and after being stored in a sealed container for a certain period of time, the 2-second value and 5-second penetration value were determined according to JIS-280B (1961). The value [10-'mm] was measured.

The physical properties of the urethane resin composition after curing are as per JISK630.
1.

The curing conditions were as follows: left at 23°C, relative humidity 50% for 7 days, and then left at 50°C for 7 days.

Example 1 370 parts of dioctyl phthalate, 500 parts of calcium carbonate, 100 parts of titanium oxide, and 10 parts of weathering stabilizer (Irganox 1010) were added to 3 liters of planetary straw mixer.
and kneaded at room temperature for 15 minutes, then kneaded at 100°C.
While kneading in a vacuum, dehydration was performed for one hour.

Next, bis[3-()ethoxysilyl)propyl 1
Tetrasulfide (BTS”) 10 parts, Frepolymer A 382 parts, β-amino-β-lactam LAC-
1, 60% cellosol acetate solution (1128 parts) was charged and kneaded for 15 minutes at room temperature.

In addition, colloidal silica WACKERHDKH-201
20 parts of xylene and 180 parts of xylene were charged and kneaded in vacuum at room temperature for 10 minutes to obtain a one-component curable polyurethane resin of the present invention.

As shown in Table 2, this urethane resin composition had no slump and had good probing properties compared to the composition using hydrophilic silica.

Furthermore, the storage stability after 14 days of closed storage at 50°C was also significantly improved, and the physical properties of the cured resin were improved.

Example 2 In a 317 knot planetary mixer, 370 parts of dioctyl phthalate, 500 parts of calcium carbonate, 100 parts of titanium oxide, and 1 part of weathering stabilizer (Irganox 1010) were added.
0 part was charged, kneaded for 15 minutes at room temperature, and then 100 parts
While kneading at 'C', a dehydration operation was carried out in a vacuum for one hour.

Next, 10 parts of bisalnoxysilyl compound A, 8603 parts of prepolymer, and 107 parts of an 80% dioctyl phthalate solution of enamine ENA,-1 were charged, and 15 parts of the solution was charged at room temperature.
I made a bunch of kons.

In addition, colloidal silica WACKERHDK+-1-2
0120 parts and 180 parts of xylene were charged, and in a vacuum,
The mixture was kneaded for 10 minutes at room temperature to obtain a one-component curable polyurethane resin of the present invention.

As shown in Table 2, this urethane resin composition had no slump and had good probing properties compared to the composition using hydrophilic silica.

Furthermore, the storage stability after 14 days of closed storage at 50°C was significantly improved, and the physical properties of the cured resin were excellent.

Example 3 In a 3 liter planetary mixer, 370 parts of dioctyl phthalate, 500 parts of calcium carbonate, 100 parts of titanium oxide, and 10 parts of weathering stabilizer (Irganox 1010) were added.
and kneaded at room temperature for 15 minutes, then kneaded at 100°
While kneading at C, a dehydration operation was carried out in a vacuum for one hour.

Next, 810 parts of bisalkoxysilyl compound and 710 parts of prepolymer C were charged and kneaded for 15 minutes at room temperature.

Furthermore, colloidal silica WACKERIIDK+7-2
The kiln was charged with 180 parts of 0.0120 parts and kneaded in a vacuum at room temperature for 10 minutes to obtain a -Y night drying type polyurethane resin of the present invention.

As shown in Table 2, this urethane resin composition had low slump and good probing properties compared to the composition using hydrophilic silica.

Furthermore, the storage stability after 14 days of closed storage at 50°C was also significantly improved, and the physical properties of the cured resin were (!).

Example 4 In Example 2, instead of bisalkoxysilyl compound A, bisalkoxysilyl compound '8! IC(BSC)
) Except for using 10 copies, all operations are done by Honshin.
- A liquid-curing polyurekne resin was obtained.

Example 5 -7 night curing polyurethane was prepared in the same manner as in Example 3, except that 10 parts of 1,3-dimethyltetramethoxydisiloxane (DTS) was used instead of bisalkoxysilyl compound B. Resin was obtained.

Comparative Example 1 A -7 night curing polyurethane resin was obtained in the same manner as in Example 1 except that 120 parts of hydrophilic colloidal silica AERO3IL #200 was used as the colloidal silica.

As shown in Table 2, this urethane resin composition has a
'C, the storage stability after 14 days of sealed storage was extremely poor.

Claims (1)

[Claims] 1. (1) polyurethane resin, (2) hydrophobic colloidal silica, and (3) the following general formula, ▲There are numerical formulas, chemical formulas, tables, etc.▼...(1) (However, the formula In the formula, R represents an oxygen atom or an alkylene bridge having 1 to 15 carbon atoms, and this alkylene bridge may be linear or branched, or may contain a heteroatom. ^2 is CH_3 or C_2H_5 or C_mH_2_m_+_1OC_2H_4 or C_m
H_2_m_+_1OC_2H_4OC_2H_4, m
represents 1 to 4, n=2 or 3. ) A thixotropic polyurethane resin composition containing a bisalkoxysilyl compound represented by: