JPH0653836B2 - Resin composition with improved stability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a resin composition having improved stability which is useful as a base resin component for paints, sealing agents, adhesives, films and the like, More specifically, it relates to a resin composition containing a specific fluoroolefin copolymer and a compound containing a 2,2,6,6-tetra-substituted piperidinyl group.

[Problems to be Solved by Prior Art and Invention]

In recent years, a fluoroolefin copolymer containing a hydroxyl group has been developed as a solvent-soluble, crosslinkable resin having excellent weather resistance, and has come to be mainly used for paints. However, the fluoroolefin copolymer containing such a hydroxyl group has a drawback that it is inferior in storage stability, thickens with time, and finally gels.

Although a method of adding a specific tertiary amine has been proposed in order to improve such a defect (Japanese Patent Laid-Open No. 28458/1985), it is necessary to add a tertiary amine to obtain sufficient stability by this method. The amount has to be increased, and there is a problem that the resin is markedly colored accordingly.

[Means for solving problems]

Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have colored the resin by adding a compound containing a 2,2,6,6-tetra-substituted piperidinyl group as an additive. The present invention has been completed by finding that it can be suppressed to a low level and the storage stability of long-term feeling can be significantly improved.

That is, the present invention is a resin with improved stability comprising (A) a hydroxyl-containing fluoroolefin copolymer and (B) a compound containing a 2,2,6,6-tetra-substituted piperidinyl group. A composition is provided.

Here, the above-mentioned fluoroolefin copolymer having a hydroxyl group is tetrafluoroethylene, chlorotrifluoroethylne, trifluoroethylene, vinylidene fluoride, monofluoroethylene, hexafluoropropylene or perfluoroalkylchirifluorovinyl ether ( However, a copolymer having a hydroxyl group bonded to the main chain and / or side chain of a copolymer having a fluoroolefin such as a perfluoroalkyl group having 1 to 4 carbon atoms) as an essential monomer component Is called.

Fluoroolefin copolymer containing such a hydroxyl group
(A) is (1) copolymerizing a vinyl monomer having a hydroxyl group with fluoroolefins as described above, or
(2) It is synthesized by a conventionally known method such as saponification of a vinyl ester group-containing polymer obtained by copolymerizing a carboxylic acid vinyl ester with a fluoroolefin, and is particularly synthesized by the method (1). Is convenient.

As a vinyl monomer having a hydroxyl group that can be used when obtaining the copolymer (A) by the method (1), hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, or hydroxyhexyl vinyl ether is used. Alkyl vinyl ethers are particularly preferable, and hydroxyalkyl esters of (meth) acrylic acid such as β-hydroxyl (meth) acrylate, β-hydroxypropyl (meth) acrylate and β-hydroxybutyl (meth) acrylate are also used. It can be used within a range that does not reduce the polymerizability.

Specific examples of other copolymerizable monomers that can be used when obtaining the copolymer (A) from the above-described fluoroolefins and vinyl monomer containing a hydroxyl group include ethyl vinyl ether and n-propyl vinyl ether. , Iso-propyl vinyl ether, n-butyl vinyl ether, iso
-Butyl vinyl ether, t-butyl vinyl ether,
Alkyl or cycloalkyl vinyl ethers such as lauryl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether or cyclohexyl vinyl ether; 2,2,3,3-tetrafluoropropyl vinyl ether, 2,2,3,3,4,4,5, 5-octafluoropentyl vinyl ether, 2,2,3,3,4,4,5,5,6,6,7,
Fluoroalkyl vinyl ethers such as 7,8,8,9,9-hexadecafluorononyl vinyl ether, trifluoromethyl vinyl ether, pentafluoroethyl vinyl ether, heptafluoropropyl vinyl ether;
Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl cyclohexanecarboxylate, vinyl benzoate, vinyl p-tert-butylbenzoate, aliphatic having a C _{8 to} C ₉ branched alkyl group Vinyl esters of carboxylic acids, vinyl carboxylates such as vinyl laurate or vinyl stearate; olefins or chloroolefins such as ethylene, propylene, vinyl chloride or vinylidene chloride; vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane There are vinylsilanes such as

If possible, it is preferable to use at least one selected from the above-mentioned monomers as cycloalkyl vinyl ether, alkyl vinyl ether, and vinyl carboxylate as another copolymerizable monomer component.

In order to obtain the copolymer (A) from the above-mentioned fluoroolefin, hydroxyalkyl vinyl ether and other copolymerizable monomer components, solution polymerization by a radical polymerization initiator system, emulsion polymerization, suspension polymerization, etc. are conventionally known. Either method can be applied.

Next, the compound (B) containing a 2,2,6,6-tetra-substituted piperidinyl group, which is the additive for improving stability used in the present invention, means the compound at least on the carbon atoms at the 2- and 6-positions. A compound containing a piperidine ring in which 4 hydrogen atoms are substituted with an organic group is designated, and at the same time when 4 hydrogen atoms at the 2nd and 6th positions are substituted with an organic group, the 1st, 3rd, 4th And a compound containing a piperidine ring substituted with at least one organic group or hydroxyl group of 7 hydrogen atoms on the 5-position nitrogen atom or carbon atom.

A typical example of the compound (B) containing such a 2,2,6,6-tetra-substituted piperidinyl group is one containing a structure represented by the following general formula (I).

^{Wherein, R 1, R 2, R} 3, R 4 each independently represents a methyl group in formula (I), an ethyl group, a propyl group, a dodecyl group, an alkyl group of C _{1 ~ 18,} such as a stearyl group; cyclopentyl Or a cycloalkyl group such as a cyclohexyl group; a substituted alkyl group such as a 2-hydroxyethyl group, a 2-methoxycarbonylethyl group, a 3-hydroxypropyl group; an allyl group such as a phenyl group, a naphthyl group, a hydroxyphenyl group; a phenethyl group, In addition to representing an aralkyl group such as a benzyl group or a hydroxyphenylalkyl group, R ¹ and R ² or R ³ and R ⁴ may be combined with each other to form a C ₃ -C ₆ aliphatic ring. Good.

Among such organic groups, from the easiness of the price point and availability, an alkyl group of C _{1 ~ 18,} especially methyl group is preferred.

Next, R ⁵ in the formula (I) is a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group and a stearyl group; a 2-hydroxyethyl group, a 2-methoxycarbonylethyl group, 2 -Acetoxyethyl group,
Substituted alkyl groups such as 2- (3-methoxycarbonylpropionyloxy) ethyl group, 3-hydroxypropyl group, etc .; Allyl groups such as phenyl group, naphthyl group, hydroxyphenyl group; further, phenethyl group, benzyl group, hydroxyphenylalkyl And an organic group represented by a cyclohexyl group.

R ⁶ in the formula (I) is a hydrogen atom, a hydroxyl group or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group and a stearyl group; a 2-hydroxyethyl group, a 2-methoxycarbonylethyl group, Substituted alkyl groups such as 2-acetoxyethyl group, 2- (3-methoxycarbonylpropionyloxy) ethyl group, 3-hydroxypropyl group; allyl groups such as phenyl group, naphthyl group, hydroxyphenyl group; phenethyl group, benzyl group, Aralkyl groups such as hydroxyphenylalkyl groups; acetoxy groups, propionyloxy groups, butyryloxy groups, lauroyloxy groups, substituted alkylcarbonyloxy groups, benzoyloxy groups, substituted benzoyloxy groups, and other ester bond-containing groups; Group, N-monoalkylcarb Bamoiruamino represents group, N, an organic group represented by the amino group-containing groups such as N- dialkylcarbamoyl amino group.

Typical examples of the compound (B) represented by the general formula (I) include 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-
Pentamethylpiperidine, 2,2,6,6-tetramethyl-4
-Hydroxypiperidine, 1,2,2,6,6-pentamethyl-
4-hydroxypiperidine, 1-ethyl-2,2,6,6-tetramethylpiperidine, 1-ethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 1-butyl-2,2,
6,6-Tetramethyl-4-hydroxypiperidine, 1-
Dodecyl-2,2,6,6-tetramethylpiperidine, 1-phenyl-2,2,6,6-tetramethylpiperidine, 1- (4
-Hydroxy-3,5-di-tert-butylphenyl) -2,
2,6,6-Tetramethylpiperidine, 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidine, 1-
(2-hydroxyethyl) -4-hydroxy-2,2,6,6
-Tetramethylpiperidine, 4-acetoxy-2,2,6,6
-Tetramethylpiperidine, 4-acetoxy-1,2,2,6,
6-pentamethylpiperidine, 1- (2-acetoxyethyl) -acetoxy-2,2,6,6-tetramethylpiperidine, 1- (2-benzoyloxyethyl) -4-benzoyloxy-2,2,6, 6-tetramethylpiperidine, 4-
Ethyl-2,2,6,6-tetramethylpiperidine, 4-ethyl-1,2,2,6,6-pentamethylpiperidine, 4-butyl-2,2,6,6-tetramethylpiperidine, 4- Octyl-
2,2,6,6-tetramethylpiperidine, 4-dodecyl-2,
2,6,6-tetramethylpiperidine, 4-stearyl-2,
2,6,6-tetramethylpiperidine, 4-stearyl-1,
2,2,6,6-Pentamethylpiperidine may be mentioned.

Furthermore, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, and 1-included as compound (B).
Hydroxyethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxyethyl-2,2,6,6-
2,2,6,6 with hydroxyl groups such as tetramethylpiperidine
-Tetramethylpiperidines succinic acid, adipic acid,
2 per molecule obtained by reacting with polybase such as sebacic acid, azelaic acid, decane-1,10-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, malonic acid, substituted malonic acid There are compounds containing the above 2,2,6,6-tetramethylpiperidine group.

Typical compounds having two or more 2,2,6,6-tetramethylpiperidine groups in one molecule are represented by the following structural formulas (II) to (VIII).

[However, n in the formula is an integer of 1 to 20. ] These piperidinyl compounds (B) can be used alone or as a mixture of two or more kinds.

The amount of the component (B) used is 0.002 of 2,2,6,6-tetra-substituted piperidinyl group per 1000 g of the component (A).
A range of equivalent to 1 equivalent is preferable. If it is less than 0.002 equivalents, the stability is insufficient, and if it exceeds 1 equivalent, coloring of the composition becomes large and it is not preferable from the economical aspect.

The composition of the present invention consisting of the component (A) and the component (B) may be in a solventless solid form, a solventless liquid form, or a solution form. Is particularly preferably a solution from the viewpoint of workability. Specific examples of the solvent that can be used when the composition of the present invention is made into a solution include aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic hydrocarbons such as hexane, octane, cyclohexane and methylcyclohexane; methanol, Alcohols such as ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; esters such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate A system; there are ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexane. Such solvents can be used alone or as a mixture of two or more kinds.

The composition of the present invention, as it is, or as necessary, a polyisocyanate compound, an amino resin, a blocked polyisocyanate compound, a polybasic acid, a curing agent such as a polybasic acid anhydride or an epoxy resin, an acrylic resin,
Use as a composition including other resins such as polyester resin or alkyd resin, pigment, leveling agent, ultraviolet absorber or antioxidant, etc. for applications such as paints, sealing agents, adhesives and films You can

〔The invention's effect〕

The composition of the present invention has a small increase in viscosity and a small color even when stored for a long period of time, resulting in a remarkable improvement in storage stability.

〔Example〕

Next, the present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples. In the following, all percentages are by weight unless otherwise specified.

Reference Examples 1 to 5 [Preparation Example of Fluoroolefin Copolymer Containing Hydroxyl Group] In a stainless pressure-resistant tube having an inner volume of 1000 ml, 330 g of methyl isobutyl ketone and 4.2 g of tert-butyl peroxypivalate were added. 1 Charge monomers as described in Table 1 and dry-ice / methanol bath-
After cooling to 70 ° C., nitrogen gas was blown in to replace the air in the pressure resistant tube.

Next, liquefied and collected hexafluoropropylene (HF
P) or chlorotrifluoroethylene (CTFE) was charged in an amount as described in the table and sealed. On the other hand,
When tetrafluoroethylene (TFE) or vinylidene fluoride (VDF) was used, each raw material was charged in the same manner as described above, TFE or VDF was press-fitted, hermetically sealed, and then weighed.

After that, each of these pressure-resistant tubes was put in a rotary constant temperature water tank heated to 60 ° C., reacted for 16 hours, then the contents were taken out, and the necessary amount of xylene was added so that the nonvolatile content became 50%. Then, each desired copolymer was obtained. The molecular weights of the obtained copolymers are as shown in Table 1, and the Gardner colors were all 1 or less.

Examples 1 to 7 A fluoroolefin copolymer (A) having a hydroxyl group and a compound (B) having a tetra-substituted piperidinyl group were mixed at a ratio shown in Table 2, and 500 ml of the mixture was mixed with 1000 ml.
Was placed in a tin can, sealed, and stored in a constant temperature bath at 40 ° C. for 3 months, and then the Gardner viscosity and Gardner color were measured. The ratio of the viscosity after storage for 3 months and the viscosity immediately after mixing was calculated and used as a scale for stable storage. The results are shown in the table.

Comparative Examples 1 to 6 Only resin solutions or hydroxyl group-containing fluoroolefin copolymers to which triethylamine was added at the ratios shown in Table 2 were stored in the same manner as in Examples to evaluate storage stability and resin color. The results are shown in the table.

Claims (4)

[Claims] 1. A resin composition having improved stability, comprising a fluoroolefin copolymer (A) containing a hydroxyl group and a compound (B) containing a 2,2,6,6-tetra-substituted piperidinyl group. object. 2. The composition according to claim 1, wherein the copolymer (A) is obtained by copolymerizing fluoroolefin and hydroxyalkyl vinyl ether as essential monomer components. object. 3. The copolymer (A), wherein at least one selected from the group consisting of fluoroolefin, hydroxyalkyl vinyl ether, vinyl carboxylate, cycloalkyl vinyl ether and alkyl vinyl ether is used as an essential monomer component. The composition according to claim 1, which is obtained by copolymerization. 4. The method according to claim 2 or 3, wherein the fluoroolefin is at least one selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylne, tetrafluoroethylene and vinylidene fluoride. Composition.