JP2949712B2 - Paint compositions and painted articles - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a coating composition and a coated article.

[Prior art] A coating composition containing a fluoropolymer as a main component is compared with a general coating composition using an acrylic resin or the like.
It is known that the durability is extremely excellent. However, a coating composition containing a fluoropolymer as a main component has a problem in workability, such as being difficult to dissolve in a solvent. Fluorine-containing copolymers that have solved these problems have already been proposed. (JP-A-53-96088). Coating compositions using these fluorinated copolymers are also known. (JP-A-55-25318, JP-A-56-21686, etc.).

Polyisocyanates or melamine-based curing agents are used in coating compositions using these fluorine-containing copolymers.

When a polyisocyanate is used, a cold-setting coating can be obtained, but the material becomes two-part, and there is a disadvantage that the two parts must be mixed at the time of use. When a melamine-based resin is used, the above-mentioned disadvantages are solved, but a high-temperature baking operation is required, and there is a problem that painting cannot be performed at a painting site or the like. Conventionally used curing agents are inferior in heat resistance as compared with fluorine-containing copolymers, so that the cured product may not sufficiently exhibit the heat resistance of the fluorine-containing copolymer.

Further, the coating composition containing a conventional fluorine-containing copolymer as a main component is preliminarily treated with a primer on the surface of the base material in order to obtain good adhesion to glass and inorganic base materials such as stainless steel. It was necessary.

Further, a coating composition comprising a mixture of a fluorine-containing copolymer having the same composition and a curing agent of silyl isocyanate has been proposed in order to solve these disadvantages. This compound has a remarkable effect in solving the above-mentioned problems.

However, when the reaction is completed, the coating film shrinks due to the reaction of decarboxylation and deammonification, and the hardness often changes over time and becomes hard.

[Problems to be Solved by the Invention] The present invention solves the above-mentioned disadvantages of the prior art. Either one-pack or two-pack types can be used.
Even when used in a one-part solution, a cured coating film can be obtained without the need for baking, and, with respect to an inorganic substrate such as glass or stainless steel, without giving a primer treatment, excellent adhesion is provided, and It is an object of the present invention to provide a coating composition which gives excellent weather resistance.

[Means for Solving the Problems] The present invention has been made to solve the above problems, and contains a polymerized unit based on a fluoroolefin,
Fluorine content is 10% by weight or more, soluble in solvents,
And a fluorine-containing copolymer having an active hydrogen-containing group or an alkoxysilyl group, and a general formula R _4-p Si (CH ₃ COO) _p [wherein R is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group , An arylalkyl group or an alkoxy group, p is an integer of 1 to 4. Where p is 1 and 3
At least one of the Rs is an alkoxy group. ]
And a polyfunctional organosilicon compound represented by the formula (1) and containing no epoxy group-containing compound.

In the present invention, the polymer contains a polymerized unit based on a fluoroolefin, has a fluorine content of 10% by weight or more, and has good compatibility or solubility with a specific organosilicon compound and a commonly used coating solvent. It is important to use a fluorine copolymer. When the fluorine content is too small, the advantage as a base of the weather-resistant paint is reduced, and not only the effect of improving the workability of the composition becomes poor, but also the characteristics of the cured coating film are not preferable. .
Further, even if the fluorine-containing polymer has a fluorine content of 10% by weight or more, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer,
Insoluble in various solvents such as tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, polychlorotrifluoroethylene, and tetrafluoroethylene-ethylene copolymer may be compatible with a specific organosilicon compound. Difficult, the entanglement of molecular chains,
This is not applicable because it is difficult to form a network structure. Usually, the fluorine content of the specific fluorinated copolymer in the present invention can be selected from the range of about 10 to 70% by weight, preferably about 15 to 50% by weight.

As the fluorinated copolymer in the present invention, an addition polymerization system is adopted from the viewpoint of simplicity of operation in the composition application step, mechanical properties of the cured coating film, and reactivity with a specific organosilicon compound. From the viewpoints such as hydroxyl group, carboxyl group, amino group, acid amide group, mercapto group,
Active hydrogen-containing groups such as silanol groups or functional groups consisting of alkoxysilyl groups (hereinafter referred to as curing reactive sites)
Is used. In particular, those containing a hydroxyl group, a carboxyl group, an amino group or an acid amide group are preferred.

In the present invention, typical examples of suitable addition polymers include tetrafluoroethylene-propylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, and further tetrafluoroethylene, chlorotrifluoroethylene or Fluoroolefins such as hexafluoropropylene and vinyl ethers, vinyl esters, allyl ethers, allyl esters, copolymers of ethylenically unsaturated compounds such as acryloyl compounds or methacryloyl compounds, and the like. From the viewpoint of a solvent-soluble addition polymer, a fluoroolefin-vinyl ether copolymer can be preferably employed.

The fluoroolefin-ethylenically unsaturated compound-based copolymer preferably usable in the present invention contains units based on a fluoroolefin and an ethylenically unsaturated compound in an amount of 30 to 70 mol% and 70 to 30 mol%, respectively.
Those having an intrinsic viscosity of about 0.05 to 2.0 dl / g measured at 30 ° C. in tetrahydrofuran in an uncured state are exemplified. As preferred fluoroolefin components, fluoroolefins having about 2 to 4 carbon atoms such as tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene, and pentafluoropropylene are employed. Ethylene, chlorotrifluoroethylene and hexafluoropropylene are preferred. Such fluoroolefins may be used alone or in combination of two or more. Preferred ethylenically unsaturated compounds include:
Vinyl ethers, vinyl esters, allyl ethers, and allyl esters are employed because of their excellent copolymerizability with fluoroolefins. Among them, alkyl vinyl ethers and alkyl allyl ethers containing a linear, branched or alicyclic alkyl group having about 2 to 15 oxygen atoms are preferred. These ethylenically unsaturated compounds may be those in which part or all of the hydrogen bonded to carbon has been replaced by fluorine. The ethylenically unsaturated monomers may be used alone or in combination of two or more.

The fluorinated copolymer in the present invention has a curing reactive site as described above. Such a curing reaction site can be introduced by the following method or the like. A method of copolymerizing a curing reactive site-containing ethylenically unsaturated compound such as hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, aminoalkyl vinyl ether, aminoalkyl allyl ether, carboxyalkyl allyl ether, acrylic acid, methacrylic acid, vinylsilane derivative, A method of copolymerizing an ethylenically unsaturated compound having an ester bond that can be hydrolyzed after polymerization and then hydrolyzing to form a hydroxyl group or a carboxyl group, a method of producing a hydroxyl group-containing fluorinated copolymer such as succinic anhydride, etc. Examples thereof include a method of forming a carboxyl group by reacting a polybasic acid anhydride.

The content ratio of the curing reactive site in the specific fluorine-containing copolymer can be appropriately changed, but if it is too small, the cross-linking reaction does not sufficiently proceed, and the cross-link density is difficult to increase, so that a tough coating film is formed. It is difficult to obtain, and if it is too large, the crosslink density becomes too large, the obtained coating film becomes brittle, and the shrinkage stress accompanying the curing reaction also increases, so that the adhesion to the substrate is low. Become smaller. Therefore, usually, as the content of the curing reactive site-containing unit,
It can be selected from the range of about 0.5 to 40 mol%, preferably about 1 to 30 mol%. When the curing reactive site is a hydroxyl group, the hydroxyl value of the fluorinated copolymer is 2 to 2.
About 200, preferably in the range of about 5 to 150,
The content ratio of the curing reactive site may be selected.

Such a fluorinated copolymer is prepared by allowing a polymerization initiator such as a polymerization initiator or ionizing radiation to act in the presence or absence of a polymerization medium on a predetermined ratio of a monomer mixture to perform a copolymerization reaction. Manufacturable.

As the polyfunctional organosilicon compound in the present invention,
A compound generally called an acyloxysilane is employed. It is essential that such an organosilicon compound has at least one acyloxy group directly bonded to silicon in one molecule. This acyloxy group is one of the functional groups referred to in the present invention. In addition to such a group, it may have a functional group capable of reacting with the curing reactive site or a group converting to a functional group capable of reacting with the curing reactive site by hydrolysis or the like. Examples of such a functional group include a hydrolyzable group directly bonded to silicon, such as an alkoxy group. It is necessary that the polyfunctional organosilicon compound has at least two functional groups including the acyloxy group. That is, when it has at least two acyloxy groups, there may be no other functional group, and when it has one acyloxy group, it has at least one other functional group. Such polyfunctional organosilicon compounds have the general formula R _4-p Si (CH ₃ COO)
_p [In the formula, R is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkoxy group, and p is an integer of 1 to 4. However, when p is 1, at least one of the three Rs is an alkoxy group. ] The polyfunctional organosilicon compound represented by the formula:
When a plurality of Rs are present (when p is 1 or 2), the plurality of Rs may be different. R is a hydrolyzable group such as an alkoxy group, or represents another organic group.
When p is 1, at least one of the three Rs must be a hydrolyzable group. If R is a hydrolysable group, it is an alkoxy group. As the alkoxy group, an alkoxy group having 4 or less carbon atoms, particularly, a methoxy group or an ethoxy group is preferable. If R is not a hydrolyzable group, it is an organic group having a carbon atom bonded to a silicon atom, ie, an alkyl group, an arenyl group, a cycloalkyl group, an aryl group, an arylalkyl group.
Preferably, an alkyl group or alkenyl group having 18 or less carbon atoms, or a phenyl group or a benzyl group which may have a substituent is employed. Most preferably, an alkyl group having 4 or less carbon atoms or a phenyl group is employed. Specifically, for example, tetraacetoxysilane: Si (CH ₃ CO
O) _{4, methyltriacetoxysilane: SiCH 3 (CH 3 COO)} 3,
Butyltriacetoxysilane: C ₄ H ₉ Si (CH ₃ COO) ₃ , Octyltriacetoxysilane: CH ₃ (CH ₂ ) ₇ Si (CH ₃ COO) ₃ ,
Ethoxy _{triacetoxysilane: C 2 H 5 OSi (CH} 3 COO) 3, phenyl triacetoxy silane: _{Vinyltriacetoxysilane: CH 2 = CHSi (CH 3} COO) 3, etc. dimethyldiacetoxysilane are exemplified.

As such a polyfunctional organosilicon compound, those having p of 2 or more, that is, those having two or more acyloxy groups directly bonded to a silicon atom are preferably used because of their excellent reactivity. In addition, p is 4 as a polyfunctional organosilicon compound.
That is, an acyloxy group directly bonded to a silicon atom
Since the curing time is extremely short for those having individual pieces, the workability may be extremely poor depending on the coating method. From the viewpoints of curing speed and coating workability, use is made only of a compound having p = 3, that is, a compound having three acyloxy groups directly bonded to a silicon atom, or p is 2 to 4, ie, acyloxy directly bonded to a silicon atom. Preference is given to using mixtures of compounds having 2 to 4 groups.

In the present invention, the polyfunctional organosilicon compounds may be used alone or in combination of two or more, or may be partially condensed.

In the composition of the present invention, an excess of the polyfunctional organosilicon compound is blended with the fluorine-containing copolymer having a curing reactive site. That is, a polyfunctional organosilicon compound having n functional groups is blended in an amount exceeding N / n mol with respect to 1 mol of the fluorine-containing copolymer having N curing reactive sites. Preferably, a polyfunctional organosilicon compound having n 'acyloxy groups is added in an amount exceeding N / n' mole. However, since the acyloxy group easily reacts with the curing reactive site, the crosslinking amount of the fluorine-containing copolymer progresses as the blending amount approaches N / n 'mol, and a high-viscosity product is generated and the final product is produced. Reactive groups required for curing the coating composition are reduced. Therefore, the lower limit of the compounding amount of the more preferable polyfunctional organosilicon compound is N / (n-1).
Mol, particularly preferably N / (n'-1) mol. When N moles of a polyfunctional organosilicon compound are blended, an average of one molecule of the polyfunctional organosilicon compound reacts per one curing reactive site of the fluorine-containing copolymer, and (n-1)
Functional groups remain. Further, when a large amount of a polyfunctional organosilicon compound of N moles or more is blended, the excess remains unreacted. The unreacted component is preferably small,
When the paint is cured, moisture and the like react with the curing agent to be cured, so that the presence of unreacted components is not particularly inconvenient. Preferably, the compounding amount of the polyfunctional organosilicon compound is not more than about 10 mol% in excess. Further, when using a normal fluorine-containing copolymer and a polyfunctional organosilicon compound, the blending amount of the latter with respect to the former is 1/100 to 100/1 by weight ratio.
The degree is preferred. Particularly preferably, it is 5/100 to 40/100 (that is, 5 to 40 parts by weight of the polyfunctional organosilicon compound per 100 parts by weight of the fluorine-containing copolymer) from the viewpoint of adhesion to the substrate and weather resistance. desirable.

When a polyfunctional organosilicon compound is blended with a fluorine-containing copolymer having a curing reactive site, the acyloxy group reacts with the curing reactive site even by simple mixing due to the high reactivity of the acyloxy group. By heating or using a catalyst, the reaction of the acyloxy group to the curing reactive site may be more positively performed. The reaction product has a functional group (acyloxy group or hydrolyzable group) derived from the polyfunctional organosilicon compound. Thus, this functional group becomes a new cure reactive site. This cure reactive site can react with water.

The coating composition of the present invention can be cured by moisture in the air. This type of coating is a so-called one-part curing type coating. The curing can also be performed using a curing agent other than water, for example, a polyol or a polyamine. In particular, it is preferable that the composition of the present invention is used for a one-part curing type paint as described above. In addition, when used for a one-part curable coating, it is preferable that the fluorine-containing copolymer and the polyfunctional organosilicon compound are sufficiently reacted in advance so that the change in the viscosity of the coating composition is small. However, when N moles or more of a polyfunctional organosilicon compound is blended with respect to 1 mole of the fluorine-containing copolymer having N curing reactive sites, gelation can be caused even by merely mixing. Absent. It is also possible to include a catalyst such as aluminum alkoxide.

The composition of the present invention preferably contains a solvent for reasons such as ease of painting. As such a solvent, various solvents can be used, such as xylene, aromatic hydrocarbons such as toluene, esters such as butyl acetate, ketones such as methyl isobutyl ketone, and glycol diethers such as diethyl cellosolve. In addition, various commercially available thinners can also be used, and these can be mixed and used in various ratios. It is desirable that such an organic solvent be appropriately selected in consideration of the state of the object to be coated, the evaporation rate, the working environment and the like.

When preparing the coating composition of the present invention, a ball mill, a paint shoer, a sand mill, a jet mill,
Various devices used for ordinary coating, such as a triple roll and a kneader, can be used. At this time, a pigment, a dispersion stabilizer, a viscosity adjusting agent, a leveling agent, an anti-gelling agent, an ultraviolet absorber, a synthetic resin or a precursor thereof can also be added. In addition, it is preferable to minimize the presence of moisture, such as moisture, when mixing. When the preparation is carried out in the presence of moisture, gelation proceeds, which may make it difficult to use as a paint.

The coating composition of the present invention has a high curing rate even when used at room temperature and becomes a coating film in a short time. However, heat drying may be used to remove and cure the solvent in a shorter time.

Further, the coating composition of the present invention can be applied not only to inorganic base materials such as glass and metal, but also to organic base materials, and can provide coated articles having excellent weather resistance.

[Action] Although the curing mechanism of the composition of the present invention is not necessarily clear, it is considered that the curing agent causes a reaction such as hydrolysis by the action of moisture in the air, and the crosslinking proceeds. Therefore, it is considered that the composition of the present invention maintains one-part curability. The cured product obtained from the composition of the present invention is considered to have extremely excellent heat resistance and weather resistance because the crosslinked structure is a stable structure. In addition, it is considered that such a crosslinked structure has a high affinity for a base material mainly composed of SiO, such as glass and enamel, so that the adhesion to the base material is increased. Furthermore, since the curing mechanism of the composition of the present invention chemically bonds to the --OH group present in the oxide layer on the surface of glass or the surface of metal, it is extremely excellent for substrates such as glass and metal. It is considered that a good adhesion is obtained.

[Examples] Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples.

The tests performed in the following Examples and Comparative Examples were performed as follows.

[Heat resistance test] The test piece was heated at 180 ° C for 8 hours. The yellow index after heating was measured with a 3M color computer manufactured by Suga Test Instruments Co., Ltd., and the difference from before heating was defined as ΔY.

4 [Adhesion Test I] After the test piece was boiled for 20 hours, a cut streak (1 mm square x 100 pieces) was put on the coating film with a cutter knife, and then a cellophane tape was pressed firmly. Thereafter, the cellophane tape was peeled off, and the number X of the remaining coating film was counted and set as X / 100.

[Solvent resistance test] The coating film of the test piece was strongly rubbed with a gauze containing xylene, and the state of the coating film was observed. This was repeated until the coating had dissolved, and the number was counted. This test was performed up to 200 times, and when dissolution of the coating film was not yet observed, the value was set to> 200.

[Storage stability] A mixture comprising a fluorine-containing copolymer, a curing agent, a solvent, and, in some cases, a curing catalyst was allowed to stand in a sealed state at room temperature, and the time until the mixture was cured was measured.

[Weather Resistance Test] The gloss retention (%) after 4000 hours of irradiation with the Sunshine Weather O-meter was measured.

Example 1 Units based on chlorotrifluoroethylene / cyclohexyl vinyl ether / ethyl vinyl ether / hydroxybutyl vinyl ether were 52.5 / 19.5 / 26.3 / 1
100 parts by weight of a fluorinated copolymer having an intrinsic viscosity of 0.20 dl / g measured in tetrahydrofuran at 30 ° C. and 15 parts by weight of methyltriacetoxysilane as a curing agent in toluene 250 parts by weight. It was mixed into parts by weight. The mixture was applied to a glass plate having a thickness of 2.5 mm with a film applicator to a dry film thickness of 25 μm,
It was left to stand for a day and cured to obtain a test piece. Table 1 shows the results of the above tests performed using the test pieces.

Comparative Examples 1 to 3 Test pieces were obtained in the same manner as in Example 1 except that the curing agent, the amount and curing conditions shown in Table 1 were used. Table 1 shows the test results using the test pieces.

Example 2 Carboxyethyl vinyl ether was used instead of hydroxybutyl vinyl ether as the fluorine-containing copolymer component (the copolymer composition was adjusted so that the molar ratio was the same as the composition of the fluorine-containing copolymer used in Example 1) ) Was obtained in the same manner as in Example 1 except that Table 1 shows the test results using the test pieces.

Example 3 Example 1 was repeated except that aminobutyl vinyl ether (the copolymer composition was equivalent to the molar ratio of the fluorine-containing copolymer of Example 1) was used instead of hydroxybutyl vinyl ether as the fluorine-containing copolymer component. A test piece was obtained in the same manner.
Table 1 shows the test results using the test pieces.

Example 4 The same procedure as in Example 1 was carried out except that instead of hydroxybutyl vinyl ether, ethylvinylsilanediol (the copolymer composition was equivalent to the molar ratio of the fluorine-containing copolymer of Example 1) was used as the fluorine-containing copolymer component. A test piece was obtained in the same manner.
Table 1 shows the test results using the test pieces.

Example 5 The same procedure as in Example 1 was carried out except that, instead of hydroxybutyl vinyl ether, trimethoxyvinylsilane (the copolymer composition was equivalent to the molar ratio of the fluorine-containing copolymer of Example 1) was used as the fluorine-containing copolymer component. A test piece was obtained in the same manner.
Table 1 shows the test results using the test pieces.

[Effects of the Invention] The composition of the present invention cures with one liquid and does not require a baking operation at a high temperature, and thus has an effect of greatly facilitating the painting operation. Further, it has an effect of exhibiting extremely excellent adhesion to a substrate such as glass or metal, and having sufficient weather resistance and extremely excellent heat resistance. Furthermore, it has the effect that the curing time is short.

Further, the coated article of the present invention does not peel off between the coating film and the article, and maintains gloss for a long period of time.

Continuation of the front page (56) References JP-A-63-210157 (JP, A) JP-A-63-243172 (JP, A) JP-A-63-196644 (JP, A) JP-A-2-38438 (JP) , A) JP-A-2-232221 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09D 127/12 C08L 27/12

Claims (3)

(57) [Claims] 1. A fluorine-containing copolymer containing a polymerized unit based on a fluoroolefin, having a fluorine content of 10% by weight or more, being soluble in a solvent, and having an active hydrogen-containing group or an alkoxysilyl group, General formula R _4-p Si (CH ₃ COO) _p
[In the formula, R is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkoxy group, and p is an integer of 1 to 4. However, when p is 1, at least one of the three Rs is an alkoxy group. And a polyfunctional organosilicon compound represented by the formula (I) and not containing an epoxy group-containing compound. 2. A fluorine-containing copolymer obtained by copolymerizing a fluoroolefin and vinyl ether, having an intrinsic viscosity of 0.05 to 2 dl / g measured at 30 ° C. in tetrahydrofuran. The composition for a paint according to claim 1. 3. A coated article comprising a cured coating of the coating composition according to claim 1 or 2.