JPS6114234A - Treating agent for molding - Google Patents

Abstract

PURPOSE:A treating agent for polymer moldings such as films and fibers, which can impart thereto durability-rich excellent antistatic and stainproof properties and improved smoothness and softness, containing specified hard and soft segments. CONSTITUTION:A treating agent for polymer moldings, containing, as an effective component, a block copolymer comprising crystalline segments, as hard segments, comprising repeating units of polyester units (e.g., polyethylene terephthalate), polyamide units (e.g., nylon 6 or 9), polyurethane units (e.g., aromatic polyurethane segments composed of an aromatic polyisocyanate and a low-MW diamine, a diol, water or the like) and a copolymer, as soft segments, comprising (A) polyalkylene ether glycol and an aliphatic polyester and (B) at least one member selected from among a reactive group-containing organosilane (e.g., gamma- glycidoxypropyltrimethoxysilane) and a reactive group-containing organopolysiloxane (e.g., a compound of the formula).

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a processing agent for molded articles, and more particularly to a processing agent useful as a surface treatment agent, surface property agent, etc. for molded articles.

"Prior Art" Hydrophobic synthetic resin molded products such as polyester and polyamide have excellent physical properties and are therefore widely used as fibers, films, and other molded products.

However, due to its hydrophobic nature, it is easy to accumulate static electricity,
T! Polymers containing ionic groups, polymers with polyoxyethylene chains, etc. are known as anti-fouling agents for water absorption and antifouling of hydrophobic synthetic resin molded products. There is.

In particular, block copolymers containing polyoxyalkylene segments and segments that have the same repeating units as the molded product are considered to be relatively durable processing agents because of their affinity for the molded products and the processing agent. (Special Public Interest Publication Act 1977-10)
(See Publication No. 794). However, although the durability of such treatment agents increases with the proportion of segments having the same repeating unit as the molded article, the durability is still unsatisfactory, and the water dispersibility and dirt removability are also reduced. This results in disadvantages such as: Further, there are also disadvantages such as a decrease in surface smoothness and a deterioration in hand feel.

"Purpose of the invention" Furthermore, the purpose is to develop a treatment agent that provides surface smoothness and flexibility with excellent durability.

"Structure of the Invention" The present invention describes a crystalline segment consisting of repeating polyester units, polyamide units and polyurethane units as a hard segment, and the following (A1) as a soft segment.
This treatment agent for polymer molded articles is characterized by containing as an active ingredient a copolymer comprising at least one type selected from the town and at least one type selected from the following group.

(A) Polyalkylene ether glycols and aliphatic polyesters.

(Bl Reactive group-containing organosilane and reactive -
group-containing organopolysiloxane.

The crystalline segment of the treatment agent in the present invention is a hard segment composed of repeating polyester units, polyamide units, and polyurethane units, and specifically, polyethylene terephthalate, polytetramethylene terephthalate, polyparaoxybenzoate, polyethylene terephthalate/ethylene isoacetate, etc. Phthalate, polyester segment mainly composed of aromatic polyester units such as polyethylene terephthalate/tetranotylene terephthalate, nylon 6, nylon 6.6, nylon 6
．． Examples include polyamide segments such as 9, nylon 6.10, and polyamides containing metaxy-1 run groups, and aromatic polyurethane segments composed of aromatic polyisocyanates and low-molecular-weight diamines, diols, water, and the like.

The number of repeating units is usually 2 to 20, preferably 8 to 20.
It is 15.

If the polymer is too high, dispersibility or dispersion stability will be impaired.
According to 81, when the repeating unit is 1, the durability is insufficient. This segment is a segment that imparts durability due to its affinity with the molded product. Therefore, although it is possible, it goes without saying that the introduction should be within the range and components that do not impair durability. In particular, when introducing an ionic group-containing component into the segment, the ionic group can be introduced into the molded product to be treated, and it can be ionically bonded to the processed molded product to improve durability, stain resistance, and adhesive properties. can be improved. In particular, it is preferable to introduce it in the case of a processing agent containing an aliphatic polyester as the soft segment A). - In addition, as the soft segment (A), polyalkylene ether glycol having an alkylene oxide repeating unit having 2 to 6 carbon atoms, such as polytetramethylene ether glycol, polypropylene ether glycol, or a copolymer of these glycols, can be used as the soft segment (A). can be mentioned. In addition, soft segments include aliphatic compounds with glycol repeating units having 2 to 6 carbon atoms, such as polyethylene sebacate, polypropylene adipate, polytramethylene adipate, polytetramethylene sebacate, and polyester consisting of dodecanedicarboxylic acid and tetramethylene glycol. Examples include polyesters and copolymers of these polyester components. Further, cyclic ester polymers such as polylactones having 4 to 8 carbon atoms can also be used. Among aliphatic polyesters, the glycol component has 8 to 8 carbon atoms.
6. The acid component preferably has 8 to 18 carbon atoms.

It is also possible to introduce an ionic group into the soft segment. The molecular weight of the soft segment is 800-1oo
oo is preferred, particularly 1000 to 5000 is more preferred.

One of the soft segments (Bl) includes reactive group-containing organosilanes and reactive group-containing diorganopolysiloxanes.At least two or more reactive group-containing organosilanes are present in the molecule, and preferably different types of It is an organosilane with a functional group, such as an alkoxy group, β
-Alkoxyethoxy group, hinyl group, methacrylic group, epoxy group, amino group, mercapto group, carboxyl group,
Organosilanes having hydroxyl groups, specifically r-glycidoxypropyltrimethoxysilane, r-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, r-aminopropyltriethoxysilane, N- β-(aminoethyl)-r-
Examples include aminopropyltriethoxysilane, β-(8,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, and vinyltris-(β-methoxyethoxy)silane. In addition, the reactive group-containing organopolysiloxane is an organopolysiloxane having at least one, preferably two or more, hydroxyl group, amino group, epoxy group, alkoxy group, carboxyl group, active hydrogen atom, etc. in the side chain or terminal. It is a siloxane, and includes, for example, a compound having the structure shown below.

RI RI KIKtRI
R1 (where R is a methyl or ethyl group, R1 is a hydrogen atom, a hydroxyl group, an alkoxy group, an aryl group,
Vinyl groups, alkyl groups having 18 or less carbon atoms, and hydrocarbon groups having substituents, such as alkoxyalkoxy groups, fluoroalkyl groups, diorganosiloxane groups, hydroxyalkyl groups, aminoerkyl groups,
These include a hyalkylaminoalkyl group, a trialkylammonium alkyl group, a mercaptoalkyl group, a carboxyalkyl group, an epoxyalkyl group, a polyoxyalkyl group, and the like. Further, R2 is a direct bond or a divalent organic group such as lower alkylene, R3 is a hydrogen atom or a lower alkyl group, and R4 is a hydrogen atom, a methyl group, or a mixed group thereof. Furthermore, n is 0 or a positive integer of 1 to 500, m is an integer of 2 to IO, and y is a positive integer of 1 to 500. ) Soft segment (Bl) is selected and used as appropriate depending mainly on the type of hard segment, the purpose of use of the processing agent, etc., but those with a structure in which reactive groups remain at the terminal or side chain even after copolymerization with the hard segment are particularly preferred. preferable.

The copolymerization ratio of hard segment and soft segment varies depending on the type of copolymer, purpose of use, etc., but the weight ratio of hard segment and soft segment is 80:20 ~
10:90 is preferred, and 70:80 to 20:80 is particularly preferred. The ratio of soft segment (A+) to soft segment (Bl) is preferably 99:1 to 10:90, particularly preferably 98:2' to 20:80.

Further, the molecular weight of the polymer is usually 2,000 or more, preferably about 5,000 to 100,000.

The co-association method varies depending on the type of hard segment and soft segment used, but for example, a method in which hard segment constituent components and soft segment components are simultaneously reacted, and a method in which the soft segment component is reacted after forming the polymer chains constituting the hard segment) Examples include a method in which Bl is reacted simultaneously or in stages, a method in which a high molecular weight polymer constituting a hard segment is produced, and then a soft segment is added and the high molecular weight polymer is depolymerized. It is also possible to indirectly bond the segments to each other by adding a reaction accelerating catalyst or using a polyfunctional crosslinking agent if necessary.

The copolymer thus obtained is used in the treatment as an organic solvent solution or an aqueous dispersion, but it can also be used alone or in a molten state with other low melting point organic compounds. To produce an aqueous dispersion, the dispersion is usually carried out by dispersing in water with the aid of an organic solvent and/or a surfactant, but depending on the composition, self-dispersion is also possible. Of course, protective colloid may be added for stabilization. Usually, aqueous dispersion is carried out using a nonionic, anionic, cationic, amphoteric, or nonionic anionic surfactant as a dispersant, but especially alkylene oxide-added ether type or ester type nonionic surfactants. Nonionic anionic surfactants such as surfactants and their terminals esterified with sulfuric acid or sulfonated with propane sultone are preferred. Specific examples of such dispersants include higher alcohols, monohydric or polyhydric alcohols and phenols such as alkylphenylphenols, alkylphenylphenols, benzylphenols, and sorbitan fatty acid esters, higher alkylamines, and higher fluorinated alcohols. 5 to 100 moles of alkylene oxide, preferably 10 to 6 moles of alkylene oxide to kilmercaptan, higher fatty acid amide, higher fatty acid, etc.
Examples include surfactants with 0 mol added thereto, salts obtained by further esterifying them with sulfuric acid, phosphoric acid, etc., and salts obtained by sulfonating them with propane sultone. When introducing an anion group, the number of moles of alkylene oxide added may be even smaller. Pluronic type and tetronic type nonionic surfactants are also preferred types of dispersants.

As a preferred dispersion method, the amount of dispersant to the copolymer is preferably 5 to 85% by weight, particularly preferably 20 to 30% by weight.
% by weight, preferably melted over an inert gas atmosphere such as nitrogen, while pre-prepared, preferably from 50 to 95 °C
It is added little by little to an alkanolamine solution, such as a 0.5 to 5% by weight aqueous solution of an alkanolamine, heated to . In this way, a milky white dispersion can be prepared.

When used alone, the copolymer has 7 excellent smoothness and flexibility, 1
．． 1. It has antifouling properties, antistatic properties, etc., but it goes without saying that other antistatic agents, antifouling agents, smoothing agents, etc. can be used in combination. In addition, if desired, stabilizers against light, heat, gas, etc., antifungal agents,
In addition to antibacterial agents, colorants, etc., inorganic fine particles such as alumina and silica can be used in combination. Further, a crosslinking agent may be used in combination.

"Effects of the Invention" The processing agent according to the present invention has excellent antistatic properties and antifouling properties that are rich in durability, and can improve smoothness and flexibility. Therefore, it is useful as a treatment agent for molded products, films, fibers, etc., or as a coating agent, paint, etc. It also has the effect of improving cloud resistance when processed into a film. When applying fiber paste, elastic properties and wrinkle recovery properties are also improved. Furthermore, by blending with a synthetic polymer, it is useful as a surface modifier for molded articles and as a binder since it improves the dispersibility of pigments and inorganic fine particles. Im! Fibers can be treated with this treatment agent at the same time as dyeing, and it is also effective in preventing fiber damage during dyeing. In addition, the treated fabric has many features such as improved sewing properties, but when treating sewing thread, defects such as thread breakage can be improved.

The present invention will be explained below with reference to Examples. Note that parts and percentages in the examples are based on weight.

Example 1゜Polyethylene terephthalate segment (repeatedly obtained molecular weight approximately 25,000 (・Ratio of hard segment 20
%) copolymer was mixed with 8 parts of polyoxyethylene lauryl ether (HLB value approximately 20) and mixed with 2 parts of a copolymer of
After melting at 50°C, the mixture was stirred into 90 parts of a 90°C monoethanolamine 1% solution prepared in advance and injected into a white emulsion. Using this dispersion, a polyethylene terephthalate jersey was coated with the copolymer. Pad it so that the adhesion amount is 1%, dry it at 100'C, and then dry it at 170'C for 2 hours.
Heat treated for minutes. The resulting treated fabric was highly elastic and wrinkle recovery was 800' (untreated 240) in the warp and weft directions.Comparative examples that did not copolymerize diorganopolysiloxane had unsatisfactory elasticity and wrinkle recovery. The angle was also inferior at 275°.

In addition, when the treated fabric was subjected to a stain removal test according to AATCC Test 180-1977, it was rated 5th grade for both olive oil and mayonnaise removal.
There was no deterioration after washing, and it had excellent antifouling properties. It also had good antistatic properties.

In addition, 1% of the above copolymer and dimethylpolysiloxane (
When treated in the same manner as above using an aqueous dispersion such that 0.5% of 5000CPS) was deposited, further improved elasticity and wrinkle recovery were obtained.

Example 2 Polyethylene terephthalate inphthalate (terephthalate: isophthalate 80:20, molecular weight approximately 125
0 )゛ and polyethylene glycol (molecule @, 200
0 ) and polytetramethylene glycol (molecule ff
i2000) (proportion of polyester segment 25%, proportion of polyethylene glycol 5%)
In the final stage of production (copolymer molecular weight approximately 10,000), 5 parts of r-glycidoxypropyljethoxysilane was added to 50 parts of the copolymer in a platinum chloride catalyst solution (H2Pt
(+6・6 H2O2g to 30d of tetrahydrofuran,
Add 0.2 parts of isopropyl alcohol (dissolved in 3 mA) and react at 260°C for 10 minutes. Add 5 parts of the 10% aqueous dispersion of the obtained copolymer, 0.02 parts of 40% dibutyltin dilaurate dispersion, and A polyester/cotton (65/35) blend fabric was padded with a treatment solution consisting of 5 parts of water (squeezing ratio 90%), and after drying (100°C),
Heat treatment was performed at 150°C for 5 minutes. The obtained treated fabric had a soft and elastic feel and had good stain resistance.

Moreover, these effects hardly changed even after 10 times of T garden washing.

Example 8 Polyethylene terephthalate 40 with a molecular weight of about 2000
part, polyethylene glyco-' having a molecular weight of about 8,000. Part 3
'J'''The following formula (11-j* is (21(D'), t
Two types of block copolymers consisting of 20 parts of tv ff helisiloxane were produced.

The obtained copolymer was emulsified and dispersed using polyoxyethylene lauryl ether (HLB approximately 15) in the same manner as in Example 1, and then used as an in-bath softener for polyester textured yarn fabrics. As a result, both of them exhibited excellent exhaust properties and produced processed fabrics with a flexible texture.

Patent applicant: Toyobo Co., Ltd. Takamatsu Oil Co., Ltd.

Claims (1)

[Claims] 1. A crystalline segment consisting of repeating polyester units, polyamide units and polyurethane units as a hard segment; at least one member selected from the following group (A) and the following group (B) as a soft segment; A processing agent for polymer molded articles, characterized in that it contains a copolymer containing at least one selected one as an active ingredient. (A) Polyalkylene ether glycol and aliphatic polyester. (B) Reactive group-containing organosilane and reactive group-containing organopolysiloxane.