JPS5953545A - Highly light-resistant latex composition - Google Patents

Abstract

PURPOSE:To obtain a composition with economically improved light resistance without degrading the characteristics of the rubber latex used, by incorporating a synthetic rubbey latex with titanium dioxide and a hindered amine-based light stabilizer. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100pts.wt. on a solid basis, of a synthetic rubber latex (e.g., carboxyl-modified styrene-butadiene latex, carboxyl-modified vinylidene chloride-styrene-butadiene latex), with (B) 1-50pts.wt. of titanium dioxide of rutile type and (C) 0.1- 3.0pts.wt. of a hindered amine light stabilizer having structure of formula (n= 2-12) [e.g., bis(2,2,6,6-tetramethyl-4-piperizine sebacate)].

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides synthetic rubber thread fibers containing titanium dioxide and
This article relates to a rubber yarn 11 composition with excellent light resistance and a hindered amine-based light-stable yarn 11.

Synthetic rubber threads, together with the amount of conjugated diene monomers, have a wide range of properties and can be used to produce films that are flexible and highly elastic, as well as hard and rigid. In particular, it has a high content of genomonomer (contains 4 genomonomers in the composition), and the chemically active double Itoyoshi combination force remains in the 1 mer chain, and this double bond can be utilized. Then, with the force of the image, a three-dimensional network AI'j structure is formed, and the elasticity, strength, and surface TF6 uniformity of the synthetic, comb thread latex film) are improved.
, c Which of the following can improve beef quality? Among these, styrene-butadiene latex has these characteristics and is cost-effective compared to other synthetic latexes, so it is used as a base coater for paper coatings and for carpets. It is used in a wide range of applications, including binders for asbenut, cement mortar admixtures, paints, adhesives, and pressure-sensitive adhesives. However, the fact that chemically active double bonds remain in the polymer main chain means that it is easily oxidized by oxygen in nitrogen, leading to aging of the film. This tendency is promoted as the temperature increases. In addition, although naturally small, it is susceptible to the effects of ultraviolet rays, and the action of sunlight not only causes yellowing, but also causes crosslinking and decomposition, leading to reductions in the physical properties of the film. These physical properties are fatal drawbacks in fields where durability is required, and limit the uses of synthetic rubber latex. For this purpose, various methods have been studied in the past. As a result, various effective anti-aging agents have been developed to improve heat resistance, and practical heat resistance has been achieved. However, although some studies have been made over the past many years to improve light control properties, they have not yet reached a practical level. If the drawbacks of light resistance of synthetic rubber latex can be improved, then compared to vinyl polymer yarn latex, especially acrylic latex which has excellent light resistance, it will have better low-temperature properties.
It can be expected to be used in a variety of applications requiring durability by taking advantage of its excellent properties of water resistance, low tackiness, and alkali resistance.

For example, acrylate latex with excellent light resistance is used as a binder for nonwoven fabrics, but
The use of the light stabilizer composition according to the present invention enables the use of synthetic rubber thread latex such as styrene/butadiene latex, and furthermore, heat resistance and light resistance are required as an automobile seat backing agent. Currently, acrylic ester-based latexes are used because of this, but with the use of light stabilizer compositions produced by Fudible IJJ, it is now possible to use synthetic rubber-based latexes, such as styrene-butadiene yarn latex. . In addition, J
Synthetic rubber latexes with improved sidelight % are advantageous in terms of cost compared to acrylic ester latexes.

Conventionally, methods such as blending acid ester latexes or copolymerization of Nisdel acrylic acid monomers have been considered to improve the light resistance of synthetic rubber latex (use of ultraviolet absorbers, acrylic). The use of UV absorbers requires a large amount of addition in order to obtain sufficient light control properties, and UV absorbers are generally expensive, so even if light resistance is improved, there is no cost advantage. In the case of cheap UV absorbers, there are problems with physical properties such as the flexibility and elasticity of the synthetic rubber latex film being lost, and it has not been put into practical use. .

In addition, it is common to blend any acrylic ester latex with excellent light control properties, but in order to obtain a practical light control property, the blending ratio of acrylic ester latex must be increased ( It is necessary to endure “C”
Even if the properties are improved, the characteristics of the synthetic rubber latex are impaired. Furthermore, a part of the conjugated diene-1-thumer was replaced with an acrylic acid Nisder monomer having excellent light resistance -C
A method of synthesizing a polymer has also been carried out, and a formulation has been found that improves the light control properties while sufficiently maintaining the characteristics of the synthetic polymer. In areas where synthetic rubber latex 't4
In areas where the characteristics of synthetic rubber are lost and the characteristics of synthetic rubber are maintained, the light control properties are insufficient, but there have been no examples of this reaching a practical level.

As a result of congratulatory research on improving the 111J properties of synthetic rubber latex, the present inventors discovered that a latex with excellent scrapability, which cannot be obtained by conventional methods, or a hynodade amine light stabilizer. By combining Lugur type dioxide technology, we discovered that a leakage can be economically advantageous and completed the present invention.

Examples of the synthetic rubber thread latex included in the latex composition with excellent stability include stereobutadiene thread copolymer latex (for example, latex L2035 manufactured by Asahi Dow Co., Ltd.), methyl methacrylate-doped diene-based Copolymer latex, acrylonitrilutadie/based copolymer latex, vinylidene chloride neuteret 7
- Conjugated diene heptamers typified by butadiene thread copolymer latex etc. and one or more co-M
Mention may be made of latexes consisting of ethylenically unsaturated monomers and, optionally, vinyl compounds having one or more copolymerizable functional groups.

Examples of conjugated diene monomers include butadiene, isoprene, chloropre-7, etc., which can be copolymerized with these conjugated diene monomers.1. c Ethylene thread unsaturated monomers are typified by aromatic vinyl compounds such as styrene, α-methylstyrene, divinylbenzene, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, etc.
Acrylic acid alkyl ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate,
Methacrylic acid alkyl esters such as octyl methacrylate, acrylonitrile, vinylidene chloride, vinyl chloride, vinyl acetate, etc. -11, ethylenically unsaturated carphones such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, etc. Acids; hydroxyalkyl acrylate-1, such as β-hydroxyethyl acrylate and hydroxyalkyl acrylate; hydroxyalkyl methacrylates, such as β-hydroxyethyl methacrylate and hydroxypropyl methacrylate; glycidyl groups, such as chrycidyl methacrylate and glycidyl acrylate; Vinyl compound with acrylamide, N-
Examples include compounds having an amide group such as methylol acrylamide. The synthetic rubber latex of the present invention can be easily obtained by a conventional emulsification method. Examples of emulsifiers used in emulsion polymerization include sodium dodecylbenzene sulfonate, sodium uryl sulfate, sodium dioctel nulphosuccinate, disodium dodecyl phenyl ether dinulphosuccinate e(7)7, an ionic emulsifier, and polyoxyether. Examples include nonionic emulsifiers such as noalkyl ether and polyoxytele/alkylphenyl ether.

A polymerization initiator (for example, persulfate or a reducing agent such as sulfite or It is possible to use a known chain transfer agent such as carbon tetrachloride or the like.

Additionally, anti-aging agents are generally added to synthetic rubber latex for the purpose of improving heat resistance. butylphenyl)butane, triethylene glycol-bis-3-(3-tertiarybutane/l
/-4-hydroxy-5-methylphenyl)flopione-), 4.4'-fuF-lite/-bis(6-terjalyptyl-m-cresol), 2.22-methylene-bis-(4 -methyl-6-tertiarybuterphenol), thiopropionic acid ester, bis[2-methyl-4-43-n-alkyl, thiopropionyloxy)-5-cusharybuterphenyl] sulfite,
One or more of commonly used compounds such as 4.4'-thiobis(6-terjawaybutyl-m-cresol) and 2-mercaptobenzimidazole can be used. Others: electrolytes, chelating agents, laxatives, pu
Modifiers, bactericides, cross-linking agents, etc. can be used as necessary.These emulsifiers, polymerization RI/!i agents, molecular weight regulators, and other auxiliary agents may be added to the MC polymerization initiator together with the monomers, or Or, a part is charged before the start of the 11th polymerization, and the rest is added continuously or discontinuously during the polymerization, or continuously or discontinuously added at the start of the polymerization in the presence or absence of a seed latex. The latex composition of ``Kienri'' is used in a known manner such as
To 100 parts by weight of the synthetic rubber latex described above, 1 to 50 parts by weight of rutile carved titanium oxide and 0.1 to 3.0 parts by weight of a hindered amine-based stabilizer are added.

The hindered amino yarn base stabilizer is bis(2,2,
6,6 tetramethyl-4-piperidine succinate,
Bis(2,2,6,6 tetramethyl-4-piperidine adipate), Bis(2,2,6,6 tetramethyl/L/-
4-biveridine azelaate), bis(2゜2,6.6
Examples include tetramethyl-4-viveridine sebaque 1-). The hindered amine light stabilizer can be added by preparing an emulsified dispersion of the stabilizer and adding this dispersion, or by dissolving it in the monomer and adding it to the polymerization system when polymerizing the synthetic rubber latex. However, if it is added to the polymerization system at the end of the polymerization when unreacted sludge remains, or if it is in powder form, it will maintain a good dispersion state (5), and even if it is left for a long time. The desired effect can also be obtained by increasing the viscosity of the latex with a thickener to prevent separation and sedimentation. is added little by little to latex containing a dispersant, and even if a thickener is added to prevent subsequent sedimentation and the latex system is thickened to an appropriate viscosity, the emulsified dispersion of titanium dioxide remains Good results can also be obtained by preparing a synthetic rubber latex, adding a thickener if necessary to prevent sedimentation and separation after standing, and thickening the latex yarn to an appropriate viscosity. As a thickener,
Examples include cellulose derivatives such as carboxyl methyl cellulose and methyl cellulose, polyvinyl alcohol, polyacrylic acid, and alkali-soluble latex. Dispersants include inorganic dispersants such as tripolylphate, anionic surfactants such as polyacrylic acid, sodium alkylnaphthalene sulfonate, polyoxyethylene sorpicone monolaurate, amylphenol decaethylene glycol, etc. Examples include nonionic surfactants.

If the amount of rutile titanium dioxide added is less than 1 part, the improvement effect on light resistance will be insufficient, and if it exceeds 50 parts, the improvement effect will reach saturation and become economically disadvantageous, making it meaningless. is 1 good.

Even in the case of hindered amine light stabilizers, the amount added is 0.
If the amount is less than 1 part, no improvement in light resistance will be observed, and if it exceeds 3.0 mfi parts, the improvement effect will reach saturation, resulting in an economical disadvantage and is meaningless. In addition, in putting the latex composition of the present invention into practice, various plasticizers, zinc white, calcium carbonate, 7V-
Fillers such as aluminum oxide, antifoaming agents, bactericidal agents, dispersants, thickeners, etc. can also be added as appropriate.

Below, examples will be given to explain the "misfire" in more detail. In addition, in the examples, parts and percentages that do not indicate percentages are:
Means Jubongbu and 1%. Furthermore, the photostability measurement method used in the Examples was carried out according to the method described below.

Light resistance measurement method 1: The latex composition according to the present invention was coated on a cotton cloth using a blade coater, and dried for 15 minutes at a temperature of 130 U in a hot air circulation box dryer.

(Coating amount---2007/ni") 2. The cotton cloth coated with the latex composition was tested using a Suga test machine (
Ltd.)l! School 7D Long Life Fedome-1-F
Using AL-3, the blank panel temperature was adjusted to 83℃, irradiated for 100 hours and 200 hours, and the degree of coloring was judged visually, and the flexibility of the coating film was judged by touch, using the following criteria. displayed.

Example 1 Latex compositions 1 to 6.5) were prepared using Asahi Dauditex L2035 according to the formulations shown in Table 1. The light resistance evaluation results of these latex compositions are shown in Table 1. As is clear from these results, the latex composition of the present invention
It can be seen that it has excellent light resistance.

Example 2 Water was first added to a droplet apparatus and a pressure-resistant polymerization vessel equipped with a stirrer.
oo part, sodium dodecylbenzene sulfonate 0.2
parts, particle size: 3 parts of German latex (styrene/butadiene-71173t 11 parts combined latex) of I old 4, 0.0 parts of sodium ethylenediaminetetraacetate. (15 parts of sodium persulfate, 2.( After adding 0.5 parts of tertiary dodecyl mercaptan and 0.7 parts of tertiary dodecyl mercaptan and thoroughly purging with nitrogen, 9()
The mixture was heated to ℃ and allowed to react for 6 hours.

A latex with an average particle diameter of JzooX and a solid content of 50% was obtained. The P II of the obtained latex was adjusted to 80 with an aqueous sodium hydroxide solution, and then water vapor and MIA blowing were performed to remove the residual upper layer 1. The solid content of the latex thus obtained was 100. Anti-aging agent, ANTAGE 3LX (manufactured by Yoro Kagaku Kogyo)
Latex A was prepared by adding 1.0 part. Using latex A, a latex composition σ was prepared according to the formulation shown in Table 2.
〇! ll was created. The light resistance evaluation results of these latex compositions are shown in Table 2. As is clear from this result,
The latex composition of the present invention has excellent light resistance!
I4].

Example 3 First, 100 ml of water was added to a pressure-resistant polymerization vessel equipped with a droplet device and a stirrer.
parts, 0.2 parts of sodium dodecylbenzenosulfonate,
3 parts of seed latex (styrene/Tsukudiene-70/30 co-monomer latex) with a particle size of 300''A, 0.05 part of sodium ethylenediaminetetraacetate, 1.0 part of sodium persulfate, and 02 parts of sodium hydroxide were charged, and then 20 parts of vinylidene chloride, 27 parts of nutyrene, 50 parts of butadiene, 3 parts of acrylic acid, and 07 parts of tertiary dodecyl mercaptan were charged, and after sufficient nitrogen purging, the mixture was heated to 90°C and reacted for 6 hours. Average particle size: 12 ( A latex with IOA, solid content of 50% was obtained. The obtained latex was adjusted to 1) H 8.0 with an aqueous sodium hydroxide solution and then subjected to steam and nitrogen blowing to remove residual monomers. Using the thus obtained latex I3, latex compositions @~■ were prepared according to the formulations shown in Table 2.

The light resistance evaluation results of these latex compositions are shown in Table 2. As is clear from these results, the latex composition of the present invention has excellent light resistance.

Example 4 Compounds 1 to 2 were prepared using Asahi Dow Latex L2035 according to the formulations shown in Table 3, and their light resistance was evaluated. The results are shown in Table 3. As is clear from these results, it can be seen that the compound composition of the present invention has excellent light resistance.

Comparative Example 1 A latex composition was prepared using Asahi Daurateknu L2035 and Latex B in Example 3 in 11 parts according to the formulation shown in Table 3, and the light resistance was evaluated. The results are shown in Table 3. As is clear from these results, when any one of rutile titanium dioxide and hindered amine light stabilizers is used in the latex composition of the present invention,
It can be seen that sufficient photostability cannot be obtained.

Comparative Example 2 A latex composition was prepared using Asahi Dow Latex L2035 and Latex B polymerized in Example 3 according to the formulation shown in Table 4. The light resistance of these latex compositions was evaluated and the results are shown in Table 4.

As is clear from these results, it can be seen that if the amount of #7J11 in either rutile titanium dioxide or hindered amine light stabilizer added to the latex composition is small, good light resistance cannot be obtained.

Comparative Example 3 Latex A polymerized in Example 2 was used to prepare a latex composition according to the formulation shown in Table 4. This σ
Noratex Composition σ] Here are the results of Lightfastness Evaluation 11.

(Hereafter, extra colors)

Claims (1)

[Claims] 1.) Synthetic rubber latex (solid content) ioo
All of M, (13 to 50 parts by weight of titanium oxide, tel.
Hindered Ami/Itomoto Lender Stabilizer 0-3.0! Latex composition 2 with excellent surface unidimensionality consisting of the i part.Claim 1, wherein the synthetic rubber latex is a carboxyl-modified stereo/-butadiene latex.
- Latex composition 3 according to item i, Claim λ, wherein the synthetic rubber latex is a carboxyl-modified vinylidene chloride-styrene-butadiene latex.
・Latex composition 4 according to item 1, claims in which titanium dioxide is in the rutile form]'
Latex composition 5 according to claim 1. Latex composition according to claim 1, in which the hindered amine thread light stabilizer has a structure represented by formula 111.