JPS6333406A - Primer composition for construction and building - Google Patents

Abstract

PURPOSE:To provide the titled composition containing a chlorinated polyolefin- containing specific vinyl polymer as an essential component and effective in improving the adhesivity to a substrate and giving high interlaminar adhesivity to intercoat and topcoat when used as a primer. CONSTITUTION:The objective primer composition contains, as an essential component, a polymer resin having a number-average molecular weight of 500-50,000 and a glass transition point of vinyl polymer component of 10-90 deg.C and produced by polymerizing (A) 5-40(wt)%, preferably 7-35% methacrylate having 4C alkyl group at side chain (e.g. n-butyl methacrylate) and (B) other vinyl monomer copolymerizable with the component A [e.g. methyl(meth) acrylate] in the presence of (C) 5-80%, preferably 10-70% chlorinated polyolefin (e.g. chlorinated polyethylene, chlorinated polypropylene-ethylene copolymer, etc.) (A+B+C is 100%).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new and useful primer composition for civil engineering and construction or building materials.

[Prior art and its problems] In recent years, lysine finishing and mastic sheathing have been increasingly applied to concrete buildings for waterproofing and aesthetic purposes.

Despite this current situation, in the various constructions that have been carried out so far, several years after construction, lysine and mastic may not adhere properly to the concrete surface, etc. Therefore, primers have traditionally been applied to inorganic materials for civil engineering and construction to improve adhesion to the main emulsion coating materials such as Inorganic Material Removal Shin and Masti 7-ri. Measures are being taken. Acrylic resins (including some crosslinked systems using urethane prepolymers), acrylic emulsion resins, vinyl chloride copolymers, and the like are used as primer compositions. However, although acrylic resin has excellent spray workability, it has poor adhesion to the main emulsion coating material. Furthermore, although acrylic emulsion resins have good adhesion to main emulsion coating materials, they have a significant drawback in water resistance. Furthermore, although vinyl chloride copolymers have good adhesion to the main emulsion coating material, they have the disadvantage of extremely poor spray workability. As described above, conventional primer compositions for civil engineering and construction have many problems that need to be solved.

[Means for Solving the Problems] Therefore, the inventors of the present invention conducted intensive studies to eliminate the drawbacks of conventional finished products, and as a result, a specific vinyl polymer containing chlorinated polyolefin was added as an essential component. By using the composition comprising the above-mentioned composition as a primer for various inorganic substrates such as concrete, ALe, calcium silicate board, or slate board, the base material emulsion coating can be applied while maintaining the level of solvent resistance, water resistance, and alkali resistance. The present invention was completed by discovering that the interlayer adhesion with the material is maintained.

That is, the present invention provides (A) in the presence of 5 to 80% by weight of a chlorinated polyolefin, (B) 40 to 5% by weight of a methacrylate having an alkyl group having 4 carbon atoms in the side chain, and (C) the above CB) I & Min. and other vinyl monomers having copolymerizability so that the total amount is 100% by weight, and the number average molecule ffi (Me) obtained by polymerization is 500 to 50.
000, and the glass transition point (Tg
) is from 10 to 80'' as an essential component.

Here, the chlorinated polyolefins (A) that can be modified to improve adhesion to the free material include ethylene, propylene, l-butene, 3-methyl-1
homopolymers or copolymers of α-olefins such as -butene, 3-methyl-1-pentene, or copolymers of α-olefins with other monomers, such as ethylene-vinyl acetate, ethylene-butadiene, A chlorinated ethylene-acrylic acid ester copolymer can be used, and chlorinated polyethylene, chlorinated polypropylene, chlorinated polypropylene-ethylene copolymer, chlorinated ethylene-vinyl acetate, etc. are suitable.

In addition, chlorinated rubber obtained by chlorinating raw rubber containing isoprene as a main component may be used, and these chlorinated polyolefins may be used alone or in a mixture of two or more.

As a commercially available chlorinated olefin, there is a product called "Super Chron" [manufactured by Yamaba Kokusaku Pulp ■], such as Super Chron 773H.

814H, 507, 510, 408, etc. In addition, there are products called "Pardren" [manufactured by Toyo Kasei Kogyo ■], such as Birden 14LLB and 15LLB.
, 35AL.

14EV etc. are mentioned. Examples of the chlorinated rubber include 7 deca chlorinated rubber CR-5, CR-10, and CR-20 (manufactured by Asahi Denka Kogyo 2). Among these, those with a high degree of chlorination are provided in powder form, and may be used after being dissolved in a known and commonly used aromatic solvent such as xylene or toluene.

The amount of chlorinated polyolefin used is in the range of 5 to 80% by weight, preferably 10 to 70% by weight, based on the vinyl polymer. If the amount of chlorinated polyolefin used is less than 5% by weight, the adhesion to inorganic materials, which is the gist of the present invention, will deteriorate. Moreover, if it is used in an amount exceeding 80% by weight, solvent resistance will be adversely affected.

Next, among the vinyl monomers used in the present invention, when a portion of methacrylate (B) having a C4 alkyl group in the side chain is used, the compatibility with the chlorinated polyolefin is improved,
Improvements are seen in the storage stability of chlorinated polyolefin-modified vinyl polymers. Examples of the methacrylate (B) having an 04 alkyl group in its side chain include n-butyl methacrylate, i-butyl methacrylate, and t-butyl methacrylate. These are one or two types
A mixture of two or more species may be used, and the amount used is 5 to 40% by weight, preferably 7 to 35% by weight. If it is less than 5% by weight, it will adversely affect the storage stability of the chlorinated polyolefin-modified vinyl polymer, and if it exceeds 40% by weight, it will adversely affect the solubility resistance.

Next, the following are representative examples of other vinyl monomers (G) that are copolymerizable with methacrylate having an 04 alkyl group in its side chain.

Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, l-propyl (meth)acrylate, 2-ethylhexyl (meth)
Acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate.

2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate.

(meth)acrylic acid esters such as dimethylaminoethyl (meth)acrylate and diethylamine ethyl (meth)acrylate; unsaturated dibasic acids such as dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, and dibutyl itaconate; dialkyl esters; (meth)acrylic acid, -7/butyl maleate,
Contains carboxyl groups such as monobutyl fumarate, crotonic acid, maleic acid, fumaric acid, and itaconic acid. t
i-mers: acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; (meth)acrylamide, N,
Carboxylic acid amide group-containing monomers such as N-dimethyl (meth)acrylamide, N-alkoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, and N-methylol (meth)acrylamide: p-styrenesulfonamide, N- Sulfonamide group-containing monomers such as methyl-p-styrenesulfonamide and N,N-dimethyl-P-styrenesulfonamide; cyano group-containing monomers such as (meth)acrylonitrile; the above (meth)acrylic acid α such as hydroxyalkyl esters of
, monomers having a phosphoric acid ester group which is a condensation product of a hydroxyalkyl ester of a β-ethylenically unsaturated carboxylic acid and a phosphoric acid or a phosphoric acid ester; p-styrenesulfonic acid, ? - Sulfonic acid group-containing monomers such as acrylamide-2-methyl-propanesulfonic acid; vinyl esters such as vinyl acetate, vinyl benzoate, "Beoba" [Product J from Shell, Netherlands; "Viscoat 8
F, 8FM, 3F or 3FN J [fluorine-containing (meth)acrylic% manufactured by Osaka Organic Chemical ■ / ? - kind]
, fluoroalkyl or perfluoroalkyl group-containing monomers such as perfluorocyclohexyl (meth)acrylate, di-perfluorocyclohexyl fumarate or N-isopropylperfluorooctanesulfonamidoethyl (meth)acrylate: vinyl chloride, chloride Examples include halogenated reflexes such as vinylidene, vinyl fluoride, vinylidene fluoride, and chlorotrifluoroethylene; and aromatic vinyl heptamers such as styrene, vinyltoluene, α-methylstyrene, and pt-butylstyrene.

These may be used alone or in combination of two or more,
The amount used is such that the total amount of components (A), (B) and (C) is 100% by weight.

In addition, a vinyl polymer portion comprising a combination of one or more of the above-mentioned methacrylate (B) having a C4 alkyl group in its side chain and another vinyl monomer (C) copolymerizable with the methacrylate (B). The glass transition point (hereinafter abbreviated as Tg) of 10-9
Use to maintain the temperature at 0℃.

The glass transition point (absolute temperature) of the copolymer is Tg, and -〇 and Tgn are the weight percent of any constituent monomer, respectively.
and the glass transition point (absolute temperature) of a homopolymer obtained from the α monomer, the relationship between these is expressed by the following empirical formula [I]. The Tg of the copolymer to be determined can be easily calculated from this formula.

1/Tg=ΣWn/Tgn [I] When the Tg of the vinyl polymer part is less than 10°C, solvent resistance deteriorates, and when it exceeds 80°C, the dried coating film becomes too hard and phenomena such as cracks appear. is also undesirable.

The thus obtained chlorinated polyolefin-modified vinyl polymer has an M. is 500 to 50,000, preferably 1
It is also necessary that the molecular weight be within the range of 500 to 35,000. If the molecular weight is lower than 500, it will not be sufficient in terms of solvent resistance, and if the molecular weight is higher than 50,000, it will be sufficient in terms of spray workability. This is not desirable as it will no longer be possible.

To prepare such a chlorinated polyolefin-modified polymer, any conventionally known polymerization method can be applied, but solution radical polymerization is the simplest method.

Typical solvents used in this case include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, and octane; methanol, ethanol,
Alcohol solvents such as l-propatol, n-7'tanol, i-butanol, 5ec-butanol, and ethylene glycol monomethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, and amyl acetate; acetone; Examples include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone, and it goes without saying that any mixture of these can also be used.

Note that the alcohol solvent is preferably used within a range that does not inhibit the solubility of the chlorinated polyolefin.

Solution radical polymerization may be carried out by a conventional method using the solvent and various radical polymerization initiators such as azo type or peroxide type. Chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid or α-methylstyrene dimer can also be used as agents.

The composition of the present invention may further include various additives such as organic or inorganic pigments, known and commonly used flow regulators, color separation inhibitors, ultraviolet absorbers, and antioxidants, as required.
Fibers like nitrocellulose and cellulose acetate butyrate! L-cord derivatives: Various resins such as petroleum resins may be added, and epoxy compounds and tin-based compounds such as dibutyltin malate may be used as stabilizers to prevent the dehydrochlorination reaction of chlorinated polyolefins.

When the coating composition obtained in this manner is applied as it is, or when the composition is made into a coating by a conventional method and applied to an object by spray, brush, roller, etc., it may be modified with chlorinated polyolefin. Adhesion to the main emulsion coating material is significantly improved compared to commercially available acrylic primers.

Here, some typical objects to be coated are:
These are inorganic substrates such as concrete, mortar, ALC, calcium silicate boards, and slate boards, and the composition has good adhesion to such inorganic materials. In addition, it can be used in living rooms with epoxy resin-polyamine paints, which are generally used as "intermediate coats" for civil engineering and construction, as well as with acrylic lacquer paints or acrylic urethane paints, which are generally used as top coats for civil engineering and construction. The interlayer adhesion of the stone has also been further improved, especially the aged stone (
(Secondary adhesion) is better than that of commercially available acrylic primers.

The composition of the present invention having such characteristics is useful not only as a primer for civil engineering and construction or building materials, but also as a one-neat system that serves as a primer and top coat.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified.

Example 1 73 parts of xylene and 14 LLB of Vertrene were added to a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a rapid flow cooler.
[Chlorinated polypropylene manufactured by Toyo Kasei Kogyo ■, non-volatile content: 1
5%] 455 parts, methyl methacrylate 29 parts, n-
1S part of butyl methacrylate, 23 parts of n-butyl acrylate and t-butylperoxyoctoate (T
0.45 part of BPO) was charged, the temperature was raised to 80° C. under a nitrogen atmosphere, and the reaction was continued at that temperature for 3 hours. Thereafter, at the same temperature, 118.75 parts of methyl methacrylate, 77 parts of n-butyl methacrylate, 11 parts of n-butyl acrylate
A mixture of 8 parts of xylene 91i and 1.9 parts of t-butyl peroxyoctoate (TBPO) was added dropwise over 4 hours. Thereafter, the reaction was continued for 10 hours at the same temperature, with a non-volatile content (NV) of 45%. 18,000, vinyl polymer portion c7) A solution of a chlorinated polyolefin-modified vinyl polymer having a Tg of 24° C. was obtained.

Example 2 800 parts of toluene and 1200 parts of Super Chron 406 (chlorinated polypropylene manufactured by Yamaba Kokusaku Valve, non-volatile content 100%) were added to the same reactor as in Example 1. After confirming that a homogeneous solution was obtained, methyl methacrylate 30
45 parts of n-butyl methacrylate, 30 parts of n-butyl acrylate, 15 parts of styrene, and 0.45 parts of t-butyl peroxyoctoate (TBPO) were charged, and the temperature was raised to 80°C under a nitrogen atmosphere. The reaction was continued for 2 hours.

Thereafter, at the same temperature, 170 parts of methyl methacrylate, n-
255 parts of butyl methacrylate, 170 parts of n-butyl acrylate, 85 parts of styrene, 422 parts of xylene and t-butyl peroxyoctoate (TBPO)
8 parts of the mixture were added dropwise over 4 hours. After that, the reaction was continued for 10 hours at the same temperature, and Mn was 12000 at NV45%.
Tgl! 9℃ 11! A solution of a vinyl-based polyolefin-modified polymer was obtained.

Example 3 800 parts of toluene, Super Chron 507 [chlorinated polyethylene manufactured by Yamaba Kokusaku Pulp ■, non-volatile content 100%] 20
0 parts, 75 parts of methyl methacrylate, 15 parts of n-butyl acrylate, 30 parts of i-butyl methacrylate and 0.45 parts of t-butyl peroxyoctoate were charged, and the dropping mixture in Example 2 was mixed with 425 parts of methyl methacrylate. , n-diptylacrylate 85 parts i-
170 parts of butyl methacrylate, 200 parts of xylene,
The same operation as in Example 2 was repeated except that 222 parts of butyl acetate, 25 parts of t-butylperoxyoctoate, and 3 parts of azobisisobutyronitrile were used to prepare NV.
M at 45%. A solution of chlorinated polyolefin modified vinyl polymer weighing 7000.7 g at 60° C. was obtained.

Example 4) /L/xn734? Ir, Super Chron 8
14H [chlorinated propylene manufactured by Sanyo Kokusaku Pulp ■, non-volatile content 60%] 166 parts, methyl methacrylate 75 parts,
15 parts of n-butyl methacrylate, 30 parts of i-butyl methacrylate, 15 parts of styrene, and 0.5 part of L-butyl peroctoate were charged, and the dropping mixture in Example 1 was mixed with 425 parts of methyl methacrylate and n-butyl methacrylate. The same operation as in Example 1 except that 85 parts of methacrylate, 170 parts of i-butyl methacrylate, 85 parts of styrene, 200 parts of xylene, 222 parts of butyl acetate, and 3.5 parts of t-butyl peroxyoctoate were used instead. Repeat this to obtain Mn 28000, 7g80 at NV45%.
A solution of a chlorinated polyolefin-modified vinyl polymer was obtained at a temperature of .degree.

Comparative Example 1 500 parts of toluene and 500 g of n-butanol were charged into the same reactor as in Example 1, and when the temperature reached 100°C, 250 parts of methyl methacrylate, 375 parts of n-butyl methacrylate, and n- Butyl acrylate 250
A mixture of 125 parts of styrene, 222 parts of butyl acetate, 3 parts of benzoic peroxide and 2 parts of t-butyl peroxyoctoate was added dropwise over 4 hours. After that, the reaction was continued for 10 hours at the same temperature with a non-volatile content of 45% and Mn.
A vinyl polymer solution weighing 23,000.7 g at 19°C was obtained.

Comparative Example 2 500 parts of xylene, 8200 parts of hard l/714LL.

66 parts of methyl methacrylate, 34.5 parts of n-butyl methacrylate, 45 parts of n-butyl acrylate and 0.5 part of t-butylperoxyoctoate were charged, and the dropping mixture in Example 1 was mixed with 374 parts of methyl methacrylate. 95.5 parts of n-butyl methacrylate, 225 parts of n-butyl acrylate, 300 parts of toluene, 252 parts of isobutyl acetate, and 6 parts of t-butyl peroxyoctoate. Repeat NV45%teMn 20000,
A solution of a chlorinated polyolefin-modified vinyl polymer having a Tg of 18° C. was obtained.

Comparative Example 3 Xylene 73811! , Birdren 141LB 455
75 parts of methyl methacrylate, 30 parts of n-butyl acrylate, 15 parts of styrene, 7.5 parts of i-butyl acrylate. B and 0.45 parts of t-butyl peroxyoctoate were charged, and the dropwise mixture in Example 1 was mixed with 425 parts of methyl methacrylate, 170 parts of n-butyl acrylate, 85 parts of styrene, and 42.5 parts of i-butyl acrylate. The same operation as in Example 1 was repeated except that 91 parts of xylene and 6 parts of t-butyl peroxyoctoate were used in place of the middle part, and Mn was 19000 with NY45%.
, 7 g of a chlorinated polyolefin-modified vinyl polymer solution weighing at 39°C was obtained.

Comparative Example 4 In a reactor similar to that used in Example 1, 333 parts of xylene,
After adding 100 parts of Super Chron 507 and confirming that it was a homogeneous solution, methyl methacrylate 45
0 parts, 270 parts of n-butyl methacrylate, 180 parts of n-butyl acrylate, and 1.8 parts of t-butyl peroxyoctoate were charged, the temperature was raised to 80°C, and the reaction was continued at the same temperature for 15 hours.

After that, it was cooled, and 883 parts of toluene was added, and the non-volatile content was 45%.
M in %. A solution of a chlorinated polyolefin-modified vinyl polymer weighing 7 g and 33° C. was obtained.

Each of the coating compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was diluted with a thinner of xylene/toluene/fhfll butyl = 50/40/10 (weight ratio) to a spray viscosity of 70X 70X. Concrete board, slate board, commercially available aluminium-free materials with a 20m layer.
Each layer was spray-painted on an ALC board to a film thickness of 15 to 2 coats.

After drying, the adhesion of each coating composition to this commercially available Im-free material was tested and this was used as data on the adhesion of each composition. A commercially available lysine paint, various tile coating materials, or a commercially available acrylic urethane paint is further applied on each coated board that has been coated and dried, and this is evaluated to determine the initial lysine adhesion to each composition and The data was taken as initial acrylic urethane adhesion data.

In addition, each coated board coated with commercially available adhesive paint or acrylic urethane paint was subjected to an accelerated weathering test for 1,000 hours using a Sunshine Weather-Ometer. Urethane adhesion was examined and used as data on adhesion over time to each coating composition.

The results are summarized in Table 1.

(The following is a blank space) [Effects of the invention] As is clear from the results in Table 1, by using the composition of the present invention as a brimer, the adhesion to the substrate is improved, and the adhesion with the intermediate coating paint is improved. This has the effect of improving interlayer adhesion with the top coat, and particularly improving adhesion over time.

Claims (1)

[Claims] (1) In the presence of (A) 5 to 80% by weight of a chlorinated polyolefin, (B) 40 to 5% by weight of a methacrylate having a C4 alkyl group in the side chain, and (C) the above (B) component. Other vinyl monomers having copolymerizability are used so that the total amount is 100% by weight, and the number average molecular weight (@M@n) obtained by polymerization is 500 to 50,
000, and the glass transition point (Tg
1. A primer composition for civil engineering and construction for inorganic materials, comprising as an essential component a polymer resin having an angle of 10 to 90°.