JP2003327903A - Moisture-curable coating material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a moisture-curable coating material composition capable of ensuring good adhesiveness to a concrete surface or a tile surface in which processing for increasing strengths of the surface is applied without removing oil in a state polluted with the oil or by a simple removal operation of oil when removing the oil. <P>SOLUTION: The moisture-curable coating material composition is composed of at least (A) a prepolymer having isocyanate groups at the ends and obtained by reacting a polyisocyanate with a polybutadiene having hydroxy groups and (B) a silane coupling agent having at least one group selected from groups consisting of isocyanate group, epoxy group, mercapto group and amino group. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-curable coating composition for painting a floor surface, wall surface, roof surface, etc., and particularly for painting a floor surface, wall surface or roof surface contaminated with oil. It relates to a suitable moisture-curable coating composition.

[0002]

2. Description of the Related Art Floors and walls of factories such as machine factories (for example, automobile repair factories) are often soiled with oil such as machine oil, which is unsuitable for painting. When painting a floor surface, wall surface, or roof surface that is contaminated with oil, the surface to be coated is contaminated with oil with a low surface tension, so use a general coating composition without removing oil. Is extremely difficult due to adhesion problems. Therefore, in general, oil is removed from the floor surface and wall surfaces before painting, but from the viewpoint of shortening the painting work process and the toxicity of the cleaning (removal) organic solvent, it is possible to perform without such a process. It is desired to develop a coating resin that adheres or adheres well to the surface to be coated that is still contaminated with oil.

To meet this demand, Japanese Patent Laid-Open No. 57-57
Japanese Patent Publication No. 12020 discloses a moisture-curable coating material composed of a predetermined prepolymer, which adheres well even if it is a surface to be coated which is contaminated with oil by directly applying it without removing oil. . Specifically, the predetermined prepolymer is a prepolymer having an isocyanate group at the terminal, which is obtained by reacting a polyisocyanate with a polybutadiene having a hydroxyl group and an average molecular weight of 400 to 1500.

However, such a moisture-curable paint has good adhesion to a normal concrete floor surface or wall surface even if it is contaminated with oil, but the surface is not subjected to any processing. On the concrete surface, tile surface, etc., it was not possible to secure sufficient adhesion when it was contaminated with oil.

[0005] In factories such as machine factories, which often handle heavy objects, it is expected that transport devices such as forklifts and machine tools will come and go, and things will be dropped. Therefore, it is particularly necessary to strengthen the floor surface. It is carried out, and the special concrete for that is used, or the surface of the concrete is given a special surface treatment. The above-mentioned problem of adhesion is particularly remarkable on the concrete surface having the reinforced surface.

[0006]

SUMMARY OF THE INVENTION Therefore, according to the present invention, even a concrete surface or a tile surface that has been subjected to processing for increasing the strength of the surface can be removed without being removed in a state of being contaminated with oil, or can be removed. Even then, it is an object of the present invention to provide a moisture-curable coating composition capable of ensuring good adhesion by a simple removal operation.

[0007]

The above object can be achieved by the present invention described below. That is, the present invention is a moisture-curable coating composition characterized by comprising at least the following components A and B.

Component A: Prepolymer having an isocyanate group at the end obtained by reacting polyisocyanate with polybutadiene having a hydroxyl group Component B: selected from the group consisting of an isocyanate group, an epoxy group, a mercapto group and an amino group. Silane coupling agent having at least one group

That is, the present invention is disclosed in JP-A-57-120.
No. 20 gazette, a concrete surface processed to increase the strength of the surface by adding the above-mentioned component B to the moisture-curable coating material having good adhesion to the oil-contaminated surface to be coated. It was possible to realize that high adhesion can be achieved even to the tile surface and tile surface. At this time, the amount of the B component is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the A component.

The moisture-curable coating composition of the present invention includes
Furthermore, it is preferable to include aggregate as the C component, and in that case, the ratio (A: C) of the amount of the A component to the amount of the C component is in the range of 10: 1 to 10:20 on a mass basis. Is desirable. Further, it is preferable that the A component and the C component are stored in separate agents in a separated state, and these are mixed immediately before coating.

When the component B is a silane coupling agent having an isocyanate group, even if the silane coupling agent is mixed with the component A, it is difficult to affect the liquid state.
The component and the B component can be stored as one agent. On the other hand, when the component B is a silane coupling agent having at least one group selected from the group consisting of an epoxy group, a mercapto group and an amino group, when the component A is mixed with any of these components, It is preferable that component A and component B are stored in separate agents in a separate state, and they are mixed immediately before coating, because the tendency of thickening is often observed.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The details of the present invention will be described below in detail with reference to preferred embodiments. The moisture-curable coating composition of the present invention is prepared by dissolving and dispersing the above-mentioned components A and B as essential components in a suitable solvent. In addition, if necessary, the component C and other additives may be included, and each of these components may be a separate and independent agent in the storage state, and it is appropriate after considering the stability of the agent. The agents may be combined in any combination, or all of them may be mixed to form one agent. Hereinafter, the moisture-curable coating composition of the present invention will be described for each of its components, and then the mode of the agent will be described.

<Component A> The component A, which is an essential component in the present invention, is a prepolymer having an isocyanate group at the terminal, which is obtained by reacting polyisocyanate with polybutadiene having a hydroxyl group.

Examples of the raw material polyisocyanate of the component A in the present invention include tolylene diisocyanate, crude tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, carbadiimidated diphenylmethane diisocyanate, phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate. Isocyanate, hexamethylene diisocyanate or the like is used, and polymethylene polyphenyl isocyanate is preferably used.

The polybutadiene having a hydroxyl group is not particularly limited, but preferably has a number average molecular weight of about 1500 or less, an average number of functional groups of 1 to 3, and more preferably 1.5 to 2. Polybutadiene having a molecular weight of more than 1500 is not preferable because the production time becomes long due to the problems of molecular weight and compatibility, and the coating film formed after coating becomes very soft. The lower limit of the number average molecular weight is generally less than 400 due to difficulty in production. On the other hand, when the average number of functional groups of polybutadiene is less than 1, the coating film formed after coating becomes very soft, and conversely 3
If it is larger than the above range, the prepolymer becomes too viscous and gels in some cases, which is not preferable.

Further, the polybutadiene having a hydroxyl group can be replaced up to 95% by mass with another ordinary polyol. Other ordinary polyols include active hydrogen-containing compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolethane, trimethylolpropane, castor oil, diglycerin, sorbitol, pentaerythritol, and dipentaerythritol. And the above-mentioned active hydrogen-containing compound and an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide or tetrahydrofuran, alone or in a mixture thereof, which is obtained by "addition polymerization""average molecular weight having two or more terminal hydroxyl groups 3, 000 or less Average number of functional groups 2 or more, preferably average molecular weight 200 to 1.00
0, active hydrogen-containing polymer having an average number of functional groups of 2 to 2.5 "
Is used. Other average molecular weights of polyester polyols, oil-modified polyester polyols, poly-ε-caprolactone polyols, acrylic polyols, polyamines, polyamides, urea fats and melamine resins, etc.
An active hydrogen-containing polymer having an average number of functional groups of 0 or less and 1.5 or more, preferably an average molecular weight of 200 to 1,000 and an average number of functional groups of 2 to 2.5 can be used in combination.

The prepolymer, which is the component A in the present invention, is a conventional polyol containing the above-mentioned polyisocyanate, the above-mentioned hydroxyl group-containing polybutadiene and optionally other active hydrogen-containing polymer at 40 ° C. under the condition of excess isocyanate. ~ 90 ° C, preferably 55 ° C to 75 ° C
In a system that blocks moisture at the temperature of
The effective NCO content is preferably 1.0 to 15% by mass, more preferably 8.0 to 13% by mass.

The above-mentioned urethanization reaction is usually carried out in an organic solvent, and examples of such a solvent include ketone solvents such as methyl ethyl ketone, ester solvents such as ethyl acetate, aromatic solvents such as toluene and xylene, and other generally. What is used as a solvent for coating is used. A catalyst may be used in the urethanization reaction. As such a catalyst, for example, a tertiary amine-based catalyst such as triethylamine or dimethylaniline, or a metal-based catalyst such as tin or zinc is used. It also serves as a catalyst when reacting with the water in the air when forming a coating film.

<Component B> The component B which is an essential component in the present invention is a silane coupling agent having at least one group selected from the group consisting of an isocyanate group, an epoxy group, a mercapto group and an amino group. Among these groups, the isocyanate group is preferable because it hardly affects the liquid state when mixed with the component A, but silane coupling agents having other groups are also stored in separate agents. However, there is no problem if they are mixed before painting. Furthermore, if long-term stability is not required, it may be mixed in advance.
These groups may have only one, but may have two or more, and in the case of two or more, they may be different groups. Further, two or more kinds of silane coupling agents may be used as the B component.

Specific silane coupling agents include:
As long as it has any of the above-mentioned functional groups, various commercially available products can be used without any problem. For example, taking the products of Nippon Unicar Co., Ltd. as examples, the following are exemplified.

(Silane coupling agent having isocyanate group) A-1310 {Chemical structure: O = C = NC ₃ H ₆ Si (O
C ₂ H ₅ ) ₃ } Y-5187 {Chemical structure: O = C = NC ₃ H ₆ Si (O
CH ₃ ) ₃ }

(Silane Coupling Agent Having Epoxy Group) A-187 {Chemical Structure is Following}

[0023]

[Chemical 1]

(Silane coupling having a mercapto group
Agent) ・ A-189 {Chemical structure: HSC₃H₆Si (OC
H₃)₃} ・ A-1289 {Chemical structure: (C₂H_FiveO)₃SiC₃H₆S_Four
C₃H₆Si (OC₂H_Five) ₃} ・ AZ-6129 {Chemical structure: HSC₃H₆Si (OCH
₃)₃}

(Silane coupling agent having amino group) A-1160 {Chemical structure: H ₂ NCONHC ₃ H ₆ Si
(OC ₂ H ₅ ) ₃ } Y-9669 {The chemical structure is the following}

[0026]

[Chemical 2]

The amounts of these B components are the same as those of the A component 1 described above.
The amount is preferably 1 to 50 parts by mass, more preferably 5 to 20 parts by mass with respect to 00 parts by mass. If the amount of the B component is too small, the effect of improving the adhesion to the concrete surface or the tile surface, which is the object of the present invention, which is subjected to the processing for enhancing the strength of the surface cannot be sufficiently exerted, while the B component If the amount is too large, not only is it economically unfavorable, but the coating suitability as a coating composition is deteriorated, whitening may occur, and the drying and curing may be delayed.

<Component C> The moisture-curable coating composition of the present invention may optionally contain an aggregate. By adding the aggregate, it is possible to reduce variations in adhesion due to the amount of dirty oil. Examples of the aggregate include cements such as Portland cement, silica sand, silica for preventing precipitation, sand, pigments, thickeners and the like.

As the amount of the C component, the ratio (A: C) of the amount of the A component to the amount of the C component is 10: 1 to 10: 1 by mass.
It is preferably in the range of 10:20, and 10: 7-1
The range of 0:12 is more preferable. If the amount of the C component is too small, the oil easily bleeds and the adhesion may vary. On the other hand, if the amount is too large, the top-coat paint may be sucked in, and pinholes may easily occur, resulting in poor finish. Each is not preferable.

<Other Additives> The moisture-curable coating composition of the present invention may optionally contain various additives such as extender pigments, colorants, thickeners, leveling agents and defoaming agents. You can also The type and amount of these additives may be determined according to the purpose, and there is no particular limitation.

<Aspect of Agent> In the moisture-curable coating composition of the present invention, the above-mentioned essential components A and B, and optionally component C and other additives are dissolved in a suitable solvent. -By dispersing, it is prepared as a paint and used for painting. It suffices that all of these components be prepared as one agent just before coating, and until then, there is no problem even if two or more agents are formed. The term "immediately before coating" as used herein does not necessarily mean that it is strictly immediately before, and even after a lapse of time such that the prepared coating material can maintain properties suitable for coating. It should be included in the previous concept.

As the usable solvent, the solvent used for the urethane reaction described in the section of the component A can be used as it is. When the B component is a silane coupling agent having an isocyanate group, it is difficult to affect the liquid state of the coating composition prepared by mixing the silane coupling agent with the A component. It can be stored as a single agent.

On the other hand, when the component B is a silane coupling agent having at least one group selected from the group consisting of an epoxy group, a mercapto group and an amino group, any one of these component B is mixed with the component A. In this case, since the tendency of thickening of the liquid is often seen, the A component and the B component are
It is preferable to store them in separate agents and mix them just before coating. When the component B is an independent agent, it may be in a solid state as it is,
It may be dissolved or dispersed in the same solvent as the solvent used for the agent containing the component A, or in a solvent having a good compatibility therewith.

When the moisture-curable coating composition of the present invention contains the component C, the aggregate which is the component C is generally insoluble in the solvent, and when it is contained together with the liquid component A, the component C is stored during storage. Since it settles or reacts with the water adsorbed on the surface of the aggregate and thickens, the A component and the C component are stored in separate agents, and It is preferable that these are mixed immediately before coating. The C component is
It can be left as it is in a solid state. When the component B is stored separately from the component A, the component B and the component C may be mixed in the powder state.

Other additives, which are optionally contained in the moisture-curable coating composition of the present invention, may be included together with the A component or the B component and the C component depending on the properties of each additive. The optimum dosage form may be selected, for example, by allowing it to be used or by using an independent agent.

<Uses> The moisture-curable coating composition of the present invention is usually coated by hand with a brush, a roller brush or the like after preparing the coating by mixing various components as described above. It is also possible to spray-paint with a machine, and the coating film formed in this way quickly dries with moisture in the air and shows sufficient adhesion to the surface to be coated which is contaminated with oil.

The moisture-curable coating composition of the present invention can be expected to have an anchoring effect (anchoring effect) when it is applied to concrete by using polybutadiene as a starting material for the component A, and has a coating film having excellent adhesion. Is obtained. Further, since the B component is added, a chemical bond is formed with the inorganic material, and therefore, the adhesion is good even for tiles and concrete whose surface is processed, for which an anchor effect cannot be expected.

The surface to be coated may be a floor surface or wall surface of oil-contaminated concrete, mortar, tile, wood or the like. In particular, the moisture-curable coating composition of the present invention exerts a high effect on a concrete surface or a tile surface which has been subjected to a treatment for enhancing the strength of the surface, in which adhesion is likely to be a problem. Here, the concrete surface that has been subjected to processing to increase the strength of the surface means that the surface has been modified by various treatments, such as one whose surface has been modified with an inorganic finishing agent containing mineral-based or metal-based aggregate, Also refers to those that are high strength or dense. For example, see “Painted floor handbook” edited by Japan Painted Floor Industry Association, p. 85-P. 91, it describes as a monolithic construction method, a penetration type floor coating construction method, a terrazzo construction method and the like. Specifically, for example, Ferrocon (registered trademark), Ferrocon (registered trademark) manufactured by ABC Corporation
Examples of the concrete-treated surface include Hard S, Ferrocon (registered trademark) Hard C, Kalakreet (registered trademark), Color Hard EM, Bescon (registered trademark) Color, Hard Namorita L, and ceramic polish.

[0039]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. <Example 1> (Preparation of agent b) Portland cement 49.0 parts by mass, silica sand 47.0 parts by mass, and silica 4.0 parts by mass were dry-mixed to prepare an agent b.

(Preparation of agent a) Using xylene as a solvent, NC
It should be 5% (external addition) on a mass basis with respect to the A component having an O percentage of 3.9% and a solid content of 35%. A agent was prepared by adding A-1310 (a silane coupling agent manufactured by Nippon Unicar Co., Ltd.), which is a B component. The obtained agent a did not show a tendency of thickening even when left in a sealed state for 7 days, and maintained a stable liquid state. No change was observed in the liquid properties even when left as it was for a total of 3 months.

(Preparation of coating material) 10 parts by mass of the obtained agent a (not left to stand) and 10 parts by weight of agent b were mixed,
The coating material of Example 1 was prepared by thoroughly stirring.

(Formation of Primer Coating Film) The obtained coating material of Example 1 was applied to a test tile piece by a brush coating method,
It was air-dried at room temperature for 3 hours to form a primer coating film having a dry film thickness of 200 μm. The test tile pieces used were those that had been subjected to the following pretreatment.・ Tile piece for test One side is mirror-like tile piece (10 × 10 cm), the surface of the mirror surface is coated with working oil (Kyodo Oil Co., Ltd., Lubcut) to a coating rate of 20 g / m ² Then, it was allowed to stand for 1.0 hour and used for the test.

(Formation of Topcoat Coating Film) As a further upper layer of the formed primer coating film, an epoxy-based paint (Floor Top # 8500, manufactured by Atomix Co., Ltd.) was applied by a brush coating method and air-dried at room temperature for 7 days. And dry film thickness 100μm
An overcoat coating film was formed.

(Adhesion test) On the coating surface of the obtained tile piece, a 2 mm square grid was cut with a cutter knife, and gum tape (cloth adhesive tape manufactured by Teraoka Seisakusho Co., Ltd.) was cut from above.
Using the same method as the usual cellophane tape peeling,
The tape was peeled off (primary adhesion). Further, the obtained tile pieces were boiled for 8 hours, naturally cooled to room temperature and dried, and then tape peeling was performed as in the above (second contact).

The evaluation indexes of the adhesion test are as follows. ⊚: The number of remaining grids after peeling the tape is 95 or more. ◯: The number of remaining grids after peeling the tape is 85 to 94. (Triangle | delta): The number of the remaining squares after tape peeling is 75-84 pieces. X: The number of remaining grids after peeling the tape is 74 or less. These results are summarized in Table 1.

<Examples 2 to 8> In Example 1, A-
13a was replaced with 1310 instead of the silane coupling agents shown in Table 1 below (all manufactured by Nippon Unicar Co., Ltd.), and agent a was prepared in the same manner as in Example 1, and then each was carried out. The paints of Examples 2-8 were prepared.
Further, a coating film was formed using each coating material in the same manner as in Example 1, and an adhesion test was conducted. These results are shown in Table 1.
Are shown together. The thickening tendency of each of the obtained agents a after standing for 7 days is also shown in Table 1 below.

<Comparative Examples 1 to 4> In Example 1, A-
13a was replaced with the silane coupling agents shown in Table 1 below (all manufactured by Nippon Unicar Co., Ltd.), and agent a was prepared in the same manner as in Example 1, and then compared with each other. The paints of Examples 1 to 4 were prepared.
Further, a coating film was formed using each coating material in the same manner as in Example 1, and an adhesion test was conducted. These results are shown in Table 1.
Are shown together. The thickening tendency of each of the obtained agents a after standing for 7 days is also shown in Table 1 below.

<Comparative Example 5> In Example 1, A-13
The agent a was prepared in the same manner as in Example 1 except that 10 was not added, and then the coating material of Comparative Example 5 was prepared. Further, using the coating material of Comparative Example 5, a coating film was formed in the same manner as in Example 1 and an adhesion test was conducted. These results are
It is summarized in Table 1. The viscosity increasing tendency of the obtained agent a after standing for 7 days is also shown in Table 1 below.

<Comparative Examples 6 to 8> Epoxy primer (Atomics Co., Ltd., Atom Primer # 800) was added with B.
5 mass% of the components A-187 (Comparative Example 6), A-189 (Comparative Example 7) and A-1289 (Comparative Example 8) (above, silane coupling agent manufactured by Nippon Unicar Co., Ltd.)
(Externally added) to prepare three kinds of agent a, then the agent b was added in the same manner as in Example 1, and Comparative Examples 6 to 6 respectively.
8 paints were prepared. Furthermore, using each paint,
A coating film was formed in the same manner as in Example 1 and an adhesion test was conducted.
These results are summarized in Table 1. The tendency of thickening of each obtained agent a after standing for 7 days is also shown in Table 1 below.
Are also shown.

[0050]

[Table 1]

<Examples 9 to 13> In Example 1 (preparation of agent a), the addition amount of A-1310 as the component B was changed to
5% by mass (external addition) to 1%, 3%, 10%, 2
Shaking to 5 levels of 0% and 55%, 5 types of agent a were prepared, and then the agent b was added in the same manner as in Example 1 to prepare coating materials of Examples 9 to 13, respectively. Further, a coating film was formed using each coating material in the same manner as in Example 1, and an adhesion test was conducted. The results are summarized in Table 2. Further, the thickening tendency of each of the obtained agents a after standing for 7 days is also shown in Table 2 below. In addition, in Table 2, as a comparison of the addition amount of A-1310 which is the B component,
The results of Example 1 and Comparative Example 5 are also shown together.

[0052]

[Table 2]

As can be seen from the above results, when coating is performed using the moisture-curable coating composition of the present invention, it is difficult to adhere to a surface such as a tile, which is disadvantageous in adhesion and is contaminated with oil. Even if there is, high adhesion can be secured.
In particular, when a silane coupling agent having an isocyanate group is used as the component B, the resulting coating material (agent a) has extremely high stability and is suitable. The above can be similarly discussed with respect to a concrete surface which is not disadvantageous in terms of adhesiveness as compared with tiles and which has been subjected to processing for increasing the strength of the surface.

[0054]

As described above, according to the present invention,
Even if the concrete surface or tile surface that has been processed to enhance the surface strength is not removed while it is contaminated with oil, or if it is removed, only a simple removal operation is required to achieve good adhesion. A secure moisture-curable coating composition can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4G028 CA01 CB05 CB08 CC03 CD01                       CD03                 4J034 DA01 DB04 DF01 DF11 DP18                       GA02 GA05 GA06 HA01 HA06                       HA07 HC03 HC12 HC13 HC52                       HC61 HC64 HC67 HC71 HC73                       MA17 RA07                 4J038 DG221 HA566 JC34 JC35                       JC36 KA03 KA08 NA12 PA20

Claims (7)

[Claims] 1. A moisture-curable coating composition comprising at least the following components A and B: Component A: Prepolymer having a terminal isocyanate group obtained by reacting polyisocyanate with polybutadiene having a hydroxyl group Component B: at least one selected from the group consisting of an isocyanate group, an epoxy group, a mercapto group and an amino group Group-containing silane coupling agent 2. The moisture-curable coating composition according to claim 1, wherein the amount of the component B is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the component A. 3. The moisture-curable coating composition according to claim 1 or 2, further comprising an aggregate as a C component. 4. A ratio of the amount of the A component and the amount of the C component (A:
The moisture-curable coating composition according to claim 3, wherein C) is in the range of 10: 1 to 10:20 on a mass basis. 5. The composition according to claim 3, wherein at least the component A and the component C are stored in separate agents, and these are mixed immediately before coating. Moisture-curable coating composition. 6. The component B is a silane coupling agent having an isocyanate group, and the component A and the component B are stored as one agent, and the component is stored as one agent. Moisture-curable coating composition. 7. A silane coupling agent in which the component B has at least one group selected from the group consisting of an epoxy group, a mercapto group and an amino group, and the component A and the component B are separated into separate agents. The method of claim 1, wherein the mixture is stored in a container, and these are mixed immediately before coating.
The moisture-curable coating composition according to any one of 5 above.