JPH07292315A - Coating material with hybrid-type prepolymer as chief agent and its production - Google Patents

Abstract

PURPOSE:To obtain the subject low-viscosity coating material good in coating circumstances by partial crosslinking between an epoxy group-bearing diluent and a hybrid-type prepolymer with a polyfunctional cyclic inorganic oxide and specific bifunctional oxirane oligomer linked to each other. CONSTITUTION:The objective coating material-contains a reaction product which can be produced by the following process: a partial crosslinking reaction is conducted in the presence of an amine-based curing agent (e.g. xylylenediamine) between a diluent having in one molecule at least two epoxy groups (e.g. N,N-diglycidyl aniline) and a hybrid-type prepolymer, a catalytic reaction product from a hydrolyzable oxygen-bearing inorganic oxide such as a polyfunctional cyclic inorganic oxide and at least bifunctional oxirane oligomer having both aromatic and aliphatic segments, having such structure that no oligomeroligomer linkage exists and the hydrolyzable oxygen of the inorganic oxide is linked to the oligomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating material containing a hybrid prepolymer as a main component, and in particular, a hybrid type prepolymer capable of adjusting the viscosity while maintaining the original physical properties. The present invention relates to a coating material containing a prepolymer as a main component and a method for producing the coating material.

[0002]

2. Description of the Related Art Recently, the hybridization of various materials has been attracting attention. According to PCT / US90 / 00370,
An inorganic oxide having hydrolyzable oxygen such as silica, and an oxirane oligomer such as a diglycigel ether of resorcinol are reacted at a predetermined temperature in the presence of an amine-based catalyst to chemically react around the inorganic oxide. Further, an organic-inorganic hybrid type prepolymer having a structure in which a plurality of oligomers are physically bonded has been disclosed.

This organic-inorganic hybrid type prepolymer has a structure which has both the characteristics of an inorganic component and the characteristics of an organic component as they are and can realize a high crosslink density. Once a material is produced, it is extremely high in chemical resistance, heat resistance, high adhesion, hardness, abrasion resistance, workability, as well as tensile strength, flexural strength, flexural modulus, elongation and water absorption. It is possible to manufacture a super coating material having physical properties.

For example, the above-mentioned PCT / US90 / 00 has already been used.
Based on the invention of 370, a hybrid type prepolymer having a structure in which at least five oxirane oligomers are bound around a cyclic silicon is used as a main agent, and the hybrid type prepolymer is mixed with ceramics subjected to a special surface treatment, Heavy-duty anticorrosion coating materials manufactured by reacting with various curing agents are being developed (US Advanced Polymer Sci
ence.Inc, trade name Siloxiran). This Si
loxiran (trade name) has resistance to most acids, alkalis and solvents, high heat resistance, low water permeability,
It had high hardness, high adhesion, high abrasion resistance, flexibility, and strong bending impact, and had excellent physical properties.

[0005]

However, the coating materials such as the above-mentioned hybrid type prepolymers or Siloxiran produced by using this as a main component are extremely high in viscosity at room temperature (about 30.000 cps), and as they are, the gold coating is not used. Since it could not be applied by means such as a roller, a spray gun or the like, an aromatic solvent such as toluene, xylene or methyl ethyl ketone is used in an amount of 4 to 6% by weight with respect to the main agent.
It has been unavoidable to add either to reduce the viscosity, or to heat the main agent up to about 80 ° C. to use it with a tendency of decreasing the viscosity.

However, the above polar solvent is extremely harmful to the human body, and particularly in the case of indoor painting work, the working environment is seriously deteriorated due to the use of the solvent. Further, even in the means for heating and lowering the viscosity, a special device has to be prepared, so that there is a problem that the mobility of the coating work is impaired. Furthermore, since the hybrid prepolymer was originally developed for heavy-duty anticorrosion coating, there was a problem that a small wave surface (lifting) phenomenon occurred on the finished surface of the coating.

Therefore, the present invention has been made in view of such a problem, and the above-mentioned PCT / US90 / 00370.
It is possible to adjust the viscosity of the coating material containing the hybrid type prepolymer obtained as a main component without diluting it with a polar solvent or heating it.
A hybrid that can be coated in a working environment temperature of ° C to about 30 ° C (the same applies hereinafter), yet does not impair the excellent physical properties of the hybrid type prepolymer as much as possible, and that can provide a good finished surface property. A coating material containing a mold prepolymer as a main component and a method for producing the same are provided.

[0008]

In order to achieve the above object, the present invention has an inorganic oxide having hydrolyzable oxygen and at least bifunctionality having an aromatic moiety and an aliphatic moiety. A hybrid prepolymer, which is a catalytic reaction product with an oxirane oligomer, characterized in that all the hydrolyzable oxygen atoms of the inorganic oxide are bonded to the oligomer without bonding between the oligomers. And a diluent containing a reaction product obtained by partially cross-linking a diluent having at least two epoxy groups in one molecule under an amine curing agent, as a main component. Succeeded in getting.

This coating material is a catalytic reaction product of an inorganic oxide having hydrolyzable oxygen and at least a bifunctional oxirane oligomer having an aromatic moiety and an aliphatic moiety. In the presence of an amine-based curing agent, 1 molecule of a hybrid type prepolymer characterized by a structure in which all the hydrolyzable oxygen atoms of the inorganic oxide are bonded to the oligomer without bonding between the oligomers It can be obtained by reacting by adding a diluent having at least two epoxy groups therein, and this reaction can be carried out at room temperature.

The above hybrid type prepolymer is PC
A prepolymer first disclosed by the invention of T / US90 / 00370, which comprises an inorganic oxide having hydrolyzable oxygen and an oxirane oligomer having an aromatic moiety and an aliphatic moiety. Is a reaction product obtained by reacting all of the hydrolyzable oxygen of the inorganic oxide, which is not cross-linked, with the oligomer in the presence of a considerable amount of an amine-based catalyst, for example, polyfunctionalized Siloxiran (: trade name, US Advanced Polymer, which has a structure in which at least five oligomers having oxirane groups are bonded to a cyclic inorganic oxide
Made by Science. Inc .; Product name in Japan: Ceraprotex,
Distributor: Tonen Corporation).

Since this hybrid type prepolymer has a structure in which a plurality of oxirane oligomers are chemically or physically bound to each other around an inorganic oxide to form a network structure, the crosslink density is very high. Therefore, it has extremely excellent physical properties as a coating material.

Preferred examples of the above inorganic oxides include metal oxides such as aluminum oxide, silica, magnesium oxide and titanium oxide. Preferred examples of the above oxirane oligomer include diglycidyl resocinol. Examples thereof include ether (DGER) and diglycidyl ether of disphenol A (DGEBA). Preferred examples of the amine-based catalyst include imidazole and imidazoline-based catalyst, and particularly preferably imidazole, 1-methylimidazole, and 2
-Methylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole and the like can be mentioned.

As the above-mentioned diluent in the present invention, it is preferable that the viscosity is lower in view of the dilution effect, but as a practically available diluent, it is about 10 cps or more.
On the other hand, if the viscosity exceeds about 300 cps, the diluting effect is extremely lowered, so it is desirable that the viscosity is about 300 cps or less.

The amount of the diluent added is preferably from 10 to 40% by weight, and more preferably from 20 to 25% by weight, based on the hybrid type prepolymer. This is because if it is within this range, a desired dilution effect can be obtained without deteriorating various physical properties.

Examples of the diluent in the present invention include the following.

That is, the viscosity is 135 to 151 cps: 2
N, N-diglycidylaniline at 5 ° C,

[0017]

[Chemical 1]

N, N-diglycidyl-O-toluidine having a viscosity of 30 to 80 cps: 25 ° C.,

[0019]

[Chemical 2]

Trimethylolpropane polyglycidyl ether having a viscosity of 120 to 150 cps: 25 ° C.,

[0021]

[Chemical 3]

Neopentyl glycol diglycidyl ether having a viscosity of 10 to 20 cps: 25 ° C.,

[0023]

[Chemical 4]

Glycerol diglycidyl ether having a viscosity of 135-151 cps: 25 ° C,

[0025]

[Chemical 5]

Glycerol triglycidyl ether having a viscosity of 155 to 175 cps: 25 ° C,

[0027]

[Chemical 6]

N = 1: viscosity 15 to 25 cps, n = 2:
Viscosity 17-27 cps, n = 3: Viscosity 15-25 cps
Polypropylene glycol diglycidyl ether (both at 25 ° C),

[0029]

[Chemical 7]

Ethylene glycol diglycidyl ether having a viscosity of 14 to 16 cps: 25 ° C.,

[0031]

[Chemical 8]

N = 2: viscosity 20 to 30 cps, n = 9:
Viscosity 80-110 cps, n = 13: Viscosity 140 cps
Polyethylene glycol diglycidyl ether (both at 25 ° C).

[0033]

[Chemical 9]

Of these, N, N-diglycidylaniline and N, N-diglycidyl-o-toluidine are preferable from the viewpoint of low viscosity characteristics.

Examples of the amine-based curing agent are as follows.

That is, 3,3-dimethyl-4,4-diaminodiphenylmethane,

[0037]

[Chemical 10]

3,3-dichloro-4,4-diaminodiphenylmethane,

[0039]

[Chemical 11]

Xylylenediamine,

[0041]

[Chemical 12]

Ethylene amines.

[0043]

[Chemical 13]

Next, the reaction in the production method of the present invention will be described.

The epoxy group is opened by the action of amine as shown in the following formula.

[0046]

[Chemical 14]

Therefore, the epoxy group constituting the diluent of the present invention is ring-opened under the amine curing agent, and the active oxygen atom of the ring-opened diluent-constituting molecule is bonded to the end group of the hybrid type prepolymer. . Here, since the diluent of the present invention has at least two epoxy groups, at least two hybrid type prepolymers are bonded via one diluent constituent molecule, and cross-linking proceeds like a net. At the same time as this reaction, the crosslinking reaction of the hybrid prepolymer proceeds due to the action of the amine-based curing agent, so that a reaction product having a high crosslinking bond density is finally produced. On the other hand, since the diluent of the present invention has an extremely low viscosity, the final viscosity of the product mixture containing the reactant can be physically reduced by mixing the diluent.

Therefore, according to the present invention, the above-mentioned various reactions promote the crosslinking reaction of the hybrid type prepolymer, and at the same time, reduce the viscosity and further crosslink the diluent for reducing the viscosity with the hybrid type prepolymer. Therefore, it is possible to suppress the deterioration of the physical properties due to the mixing of the diluent.

[0049]

【Example】

(Production of hybrid type prepolymer) 2724 g of liquid resin of diglycigel ether of resorcinol and 409 g of diethyl-4-methylimidazole as a catalyst.
And were added to the reactor and sent to a high shear stirrer. In a high shear stirrer, stir these to a temperature of 80 ° C,
When the temperature reached 80 ° C or higher, 3405 g of silica having an average particle size of 4 microns was added to the reactor, and further 3000 r
The temperature was raised to 150 ° C over 3 hours while stirring at pm (3000 rpm for 1 minute). When the temperature of the solution changed, the heating of the reactor was stopped, and after stirring for 1 hour, the reaction product was taken out of the reactor. The physical properties of the produced hybrid type prepolymer were as follows.

・ Color Dark yellowish brown ・ Viscosity (77 ° C) 3500 cps ・ Nonvolatile matter 99.99 ・ Specific gravity 1.29 to 1.32 ・ Epoxy equivalent 165 to 180 ・ Precipitate (wt%) <0.1 As for the viscosity, it is a measured value at 77 ° C, and if it is cooled to room temperature (20 ° C), it rises to around 30,000 cps.)

(Manufacturing Experiment of Coating Material Using Hybrid Prepolymer as Main Component) Siloxiran (trade name) 10
To 0 (parts by weight), 20 (parts by weight) and 25 (parts by weight) of neopentyl glycol diglycidyl ether were added as diluents, respectively, and 25 (parts by weight) of the modified aliphatic polyamine as a curing agent was added thereto. In addition, the mixture was stirred at 25 ° C. until a sufficiently uniform mixed state was obtained to obtain a coating material A and a coating material B, and their physical properties were tested. In addition, as a comparative example, modified aliphatic polyamine 40 (weight) was added to liquid epoxy resin 100 (weight part), and this was applied to coating materials A and B.
Similarly to the above, an epoxy solvent-free anticorrosion coating material X was prepared which was stirred at 20 ° C. In Table 1 below, the physical properties of coating material A, coating material B (present invention) and coating material X are compared. The chemical resistance value shows the change in weight after 7 days of immersion in various chemicals at 20 ° C.

[0052]

[Table 1]

Thus, both coating materials A and B have a viscosity range (2500) which can be suitably used as a coating material at room temperature.
Despite the decrease in viscosity up to 3000 cps), pencil hardness, Shoreo hardness, chemical resistance (concentrated sulfuric acid, 6
It was confirmed that the physical properties of 0% sulfuric acid, acetone, methyl ethyl ketone, etc. were extremely excellent.

[0054]

As described above, according to the present invention, the viscosity can be significantly reduced as compared with the hybrid type prepolymer, and a coating material that can be coated at room temperature can be obtained. At this time, since it is not necessary to use a polar solvent as in the conventional case, it is possible to greatly diminish hygiene problems for the human body including the coating environment. Further, it is not necessary to prepare a device such as a heat-up device in order to reduce the viscosity.

Further, according to the present invention, since the network structure including the diluent is formed by the cross-linking reaction accompanying the use of the diluent, it is possible to retain the high physical properties originally possessed by the hybrid prepolymer.

Further, according to the present invention, since the viscosity of the coating material can be adjusted by selecting the diluent and adjusting the mixing amount thereof, it is possible to prevent the lifting phenomenon from occurring on the coated surface. You can also do it.

At the same time, the amount of the hybrid prepolymer, which is considerably expensive, can be reduced, and the economic benefits of cost reduction can be enjoyed.

Claims (15)

[Claims] 1. A catalytic reaction product of an inorganic oxide having hydrolyzable oxygen and an oxirane oligomer having at least bifunctionality having an aromatic moiety and an aliphatic moiety, wherein the oligomers are of the same type. A hybrid prepolymer characterized by a structure in which a hydrolyzable oxygen atom of the inorganic oxide is bonded to the oligomer without being bonded, and a diluent having at least two epoxy groups in one molecule, A coating material whose main component is a hybrid type prepolymer containing a reaction product formed by partially crosslinking under an amine curing agent. 2. The hybrid prepolymer comprises an inorganic oxide having hydrolyzable oxygen and an oxirane oligomer having an aromatic moiety and an aliphatic moiety, which are not crosslinked between the oligomers but are inorganic. The hybrid prepolymer as a main component according to claim 1, which is a reaction product obtained by reacting all of the hydrolyzable oxygen of the oxide with the oligomer in the presence of a considerable amount of an amine-based catalyst. Coating material. 3. The hybrid prepolymer according to claim 1, wherein the hybrid prepolymer is a hybrid prepolymer in which at least five oligomers having an oxirane group are bonded to a polyfunctionalized cyclic inorganic oxide. A coating material whose main ingredient is the hybrid type prepolymer. 4. The coating material containing a hybrid prepolymer as a main component according to any one of claims 1 to 3, wherein the diluent has a viscosity of 10 to 300 cp. 5. The main component of the hybrid prepolymer according to claim 1, wherein the amount of the diluent is equivalent to 20 to 25% by weight of the hybrid prepolymer. Coating material. 6. The diluent is N, N-diglycidylaniline, N, N-diglycidyl-O-toluidine, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, glycerol diglucidyl. The hybrid prepolymer according to any one of claims 1 to 5, which is one or more of ether, glycerol triglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether. A coating material whose main ingredient is. 7. The amine-based curing agent is any one of 3,3-dimethyl-4,4-diaminodiphenylmethane, 3,3-dichloro-4,4-diaminodiphenylmethane, xylylenediamine and ethyleneamines, or A coating material containing, as a main component, the hybrid prepolymer according to claim 1, which is two or more. 8. A catalytic reaction product of an inorganic oxide having hydrolyzable oxygen and an oxirane oligomer having at least bifunctionality having an aromatic moiety and an aliphatic moiety, wherein the oligomers are in the same space. To a hybrid type prepolymer characterized by a structure in which a hydrolyzable oxygen atom of the inorganic oxide is bonded to the oligomer without being bonded to the oligomer, in the presence of an amine-based curing agent, at least two A method for producing a coating material containing a hybrid prepolymer as a main component, which is obtained by adding and reacting a diluent having an epoxy group. 9. The method for producing a coating material containing a hybrid prepolymer as a main component according to claim 8, wherein the reaction is carried out at room temperature. 10. The hybrid prepolymer comprises:
An inorganic oxide having hydrolyzable oxygen and an oxirane oligomer having an aromatic part and an aliphatic part are not cross-linked between the oligomers, but all the hydrolyzable oxygen of the inorganic oxide is concerned. The method for producing a coating material containing a hybrid prepolymer as a main component according to claim 8 or 9, which is a reaction product obtained by reacting in the presence of a considerable amount of an amine-based catalyst for binding with an oligomer. 11. The hybrid prepolymer comprises:
The hybrid prepolymer according to any one of claims 8 to 10, which is a hybrid prepolymer in which at least five oligomers having an oxirane group are bonded to a polyfunctionalized cyclic inorganic oxide. The manufacturing method of the coating material. 12. The diluent has a viscosity of 10 to 300 cp.
The method for producing a coating material containing the hybrid prepolymer as a main component according to any one of claims 8 to 11, wherein the coating material is s. 13. The method for producing a coating material containing a hybrid prepolymer as a main component according to claim 8, wherein the diluent is added as a hybrid prepolymer in an amount of 20 to 25% by weight. 14. The diluent is N, N-diglycidylaniline, N, N-diglycidyl-O-toluidine, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, glycerol diglucidyl. The hybrid prepolymer according to any one of claims 8 to 13, which is one or more of ether, glycerol triglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether. The manufacturing method of the coating material which uses as a main ingredient. 15. The amine-based curing agent is any one of 3,3-dimethyl-4,4-diaminodiphenylmethane, 3,3-dichloro-4,4-diaminodiphenylmethane, xylylenediamine and ethyleneamines, or The method for producing a coating material containing, as a main component, the hybrid prepolymer according to any one of claims 8 to 14, which is two or more.