JP2009235628A - Suede-like artificial leather excellent in flame retardancy and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel flame retardant suede-like artificial leather capable of adding flame retardancy conforming to JIS A 1091 A-2 method (45° Meckel burner method) section 3 by treating with a non-halogen flame retardant without a halogen-based flame retardant, excellent in light resistance on the surface side and the back side, generating little dark stain on the surface side and the back side, and being hardly scratched on the surface applied with the flame retardant composition, and to provide a method for producing the same. <P>SOLUTION: The suede-like artificial leather has a weight per unit area of ≥450 g/m<SP>2</SP>and is added with a flame retardant compound A containing a phosphorus atom or nitrogen atom, a flame retardant composition B made of an ammonium polyphosphate, a phosphate ester, a fluorine-based water repellent, a light resistance-improving agent and a binder resin which is a water dispersion of a polyester resin on one surface and, in addition, a protection layer comprising the binder resin which is the water dispersion of the polyester resin on the upper layer of the flame retardant composition B. The method for producing the suede-like artificial leather excellent in flame retardancy is to treat a thermoplastic synthetic fiber fabric formed of a woven fabric, a knit fabric or a nonwoven fabric having raised nap on the surface and impregnated with a polyurethane resin by carrying out the following steps (a)-(c): (a) a step of adding the flame retardant compound A; (b) a step of adding the flame retardant composition B on one surface; and (c) a step of adding the protection layer comprising the binder resin which is the water dispersion of the polyester resin same as that used in the step (b) on the upper layer of the flame retardant composition B. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a suede-like artificial leather excellent in flame retardancy and a method for producing the same.

  More specifically, it is an artificial leather based on a woven fabric, a knitted fabric or a non-woven fabric in which a polyurethane synthetic resin is impregnated with a thermoplastic synthetic fiber fabric having raised or raised surfaces, and without using a halogen-based flame retardant, It has good flame retardancy, is excellent in light fastness on the front and back sides of the fabric, is less likely to cause stickiness on the front and back sides of the fabric, and has scratches on the coated surface of the flame retardant composition The present invention relates to a suede-like artificial leather that is difficult to stick and has excellent flame retardancy, and a method for producing the same.

  In this case, in the suede-like artificial leather to which a flame retardant composition is applied, the wetted part of the suede-like artificial leather when it is naturally dried after the moisture represented by water droplets adheres from the front side and the back side. Refers to the phenomenon of white spots or stains.

  Conventionally, a suede-like artificial leather in which napped surfaces of thermoplastic synthetic fibers are formed on the surface by buffing the surface of a nonwoven fabric, woven fabric or knitted fabric made of ultrafine thermoplastic synthetic fibers impregnated with a polymer elastic body such as polyurethane, It has been widely deployed as a luxury clothing material.

  In recent years, such suede raised artificial leather is used not only for clothing but also for materials, for example, vehicle interior materials such as car seats and linings of luxury automobiles, furniture such as chairs and walls, and interiors. Development for building materials is being carried out.

  In these non-garment fields, in particular, it may be required to have excellent flame retardancy.

  For this reason, overcoming the following problems (1) to (4) unique to suede-like artificial leather, which is not found in ordinary woven or knitted fabric made of synthetic fibers, etc. Various studies have been conducted with the goal of this.

(1) There is a space between the raised hairs and it is structurally flammable.
(2) The flame retardant mechanism is different between the polymer elastic body and the thermoplastic synthetic fiber.
(3) The flame retardant deteriorates the surface appearance, surface quality and light resistance of the suede raised artificial leather.
(4) The flame retardant processing induces a decrease in dyeing fastness and a texture hardening.

  As a method for solving the problems (1) to (4) described above, there has been proposed a method in which a halogenated phosphoric ester is applied to the back side of the napped surface together with an acrylic ester resin (see Patent Document 1). .

  Further, a method has been proposed in which a flame retardant is included in advance in a polymer elastic body such as polyurethane impregnated in a nonwoven fabric or the like (see Patent Document 2).

  Furthermore, a method of using a thermoplastic synthetic fiber copolymerized with an organic phosphorus component has also been proposed (see Patent Document 3).

  However, the method of Patent Document 1 in which the halogenated phosphate ester is applied to the back surface side of the raised surface together with the acrylic ester resin is excellent in flame retardancy, but naturally contains halogen atoms. In recent years, environmental effects of halogen-based flame retardants have been regarded as a problem, and development of non-halogen-based flame retardants has been urgently performed. However, such requests cannot be met.

  Further, in the method of Patent Document 2 in which a polyurethane impregnated in a non-woven fabric is preliminarily incorporated with a flame retardant, the flame retardant may decrease the degree of polyurethane polymerization over time and may become brittle. Later, there was a problem that the strength of the suede-toned artificial leather was deteriorated, and not only the tear, peach, and residual distortion were caused, but also the light fastness of dyeing was lowered.

  Furthermore, in the method of Patent Document 3 in which a thermoplastic synthetic fiber copolymerized with an organic phosphorus component is used, there is a problem of a decrease in physical properties such as a decrease in strength over time and hydrolysis, which are characteristic of the copolymer fiber.

  In addition, as a suede-like fiber structure that has excellent flameproofness with self-extinguishing properties, has a good texture, does not deteriorate dyeing fastness, and is difficult to generate toxic gases such as dioxin during incineration, A suede-like fiber structure in which a thermoplastic synthetic fiber fabric having a raised portion on the surface is provided with a resin composition containing an acrylic ester resin as a main component and an aromatic phosphate compound and a metal oxide. The thing is proposed (refer patent document 4).

  Furthermore, as a suede-like fiber structure excellent in flameproofing and fusible properties, that is, it has self-extinguishing properties, excellent flameproofing and fusible properties, good texture and low dyeing fastness In addition, a suede-like fiber structure having a napped portion on its surface as a suede-like fiber structure that hardly generates toxic gases such as dioxins during incineration, and the suede-like fiber structure has an acrylate ester A resin and an organic fluorinated polymer water repellent are provided, and an acrylic ester resin composition containing an aromatic phosphate compound and a metal oxide is attached to the back surface of the suede-like fiber structure. A suede-like fiber structure is proposed (see Patent Document 5).

  In addition, as a flame-retardant napped artificial leather composed of synthetic fibers which are excellent in flame retardancy, light resistance and wear durability and are non-halogen, woven fabrics, knitted fabrics containing synthetic fibers having a single fiber fineness of 1 dtex or less, or Non-woven fabric and at least one phosphate compound selected from guanidine phosphate, ammonium polyphosphate, melamine polyphosphate and phosphate amide, pentaerythritol, dipentaerystol, melamine, on one side of a fabric comprising a polymer elastic body, An artificial leather to which a flame retardant composition containing at least one compound selected from dicyandiamide, starches, celluloses, and sorbitol and a binder resin has been provided has been proposed (see Patent Document 6).

  However, the flame retardant technology disclosed in Patent Document 4 and Patent Document 5 uses an acrylate resin, and therefore satisfies the criteria of JIS A 1091 A-2 method (45 ° Meckel burner method) Category 3. It is difficult.

  Moreover, in the flame retarding technique disclosed in Patent Document 6, there is a problem that significant sticking occurs when moisture adheres to the back side to which the flame retardant composition is applied.

JP 58-013786 A Japanese Patent Laid-Open No. 7-18484 JP 2002-294571 A JP 2004-36011 A JP 2004-308051 A JP 2005-2512 A

  The object of the present invention is to solve the above-mentioned conventional technology by treating with a so-called non-halogen flame retardant without using a halogen flame retardant, and by JIS A 1091 A-2 method (45 ° Meckel burner). Act) Can provide flame retardancy conforming to Category 3, has excellent light resistance on the front side and back side, has less occurrence of sticking on the front side and back side, It is an object of the present invention to provide a novel flame-retardant suede-like artificial leather that hardly scratches the coated surface and a method for producing the same.

  The suede-like artificial leather excellent in flame retardancy of the present invention that achieves the above-mentioned object has the following configuration (1).

(1) A suede-like artificial leather having a basis weight of 450 g / m ² or more, provided with a flame retardant compound A containing phosphorus or nitrogen atoms, and further having ammonium polyphosphate, phosphoric acid on one side A flame retardant composition B composed of an ester, a fluorine-based water repellent, a light resistance improver, and a binder resin that is an aqueous dispersion of a polyester resin is provided, and further on the applied flame retardant composition B, A suede-like artificial leather excellent in flame retardancy, which is provided with a protective layer made of a binder resin which is an aqueous dispersion of the polyester resin.

  Moreover, in the suede-like artificial leather excellent in flame retardancy of the present invention, as a more preferable specific configuration, it is composed of any of the following configurations (2) to (8).

ここで、Ｘ；０，１ (2) The flame retardant compound A contains at least one selected from the group consisting of guanidine phosphate, guanidine sulfamate and a cyclic phosphonate ester represented by the following general formula [1]. (1) The suede-like artificial leather having excellent flame retardancy.

Where X; 0, 1

(3) The suede-like artificial leather excellent in flame retardancy according to the above (1) or (2), wherein the phosphate ester is bisphenol A bisdiphenyl phosphate.

(4) The flame retardant according to any one of (1) to (3) above, wherein the fluorine-based water repellent is a perfluoroalkyl group- or perfluoroalkenyl group-containing acrylic copolymer. Suede artificial leather.

(5) The light resistance improver contains at least one selected from a benzotriazole-based ultraviolet absorber and a semicarbazide-based light stabilizer, according to any one of the above (1) to (4), Suede-like artificial leather with excellent flame resistance.

(6) In the binder resin, which is an aqueous dispersion of a polyester resin, the polyester resin as a solid content is a polymer compound composed of an acid component and an alcohol component, and sulfophthalic acids are used as acid components used during polymerization. And an aliphatic dicarboxylic acid as an alcohol component, an aliphatic polyhydric alcohol is contained, and the suede-like artificial material having excellent flame retardancy according to any one of the above (1) to (5) leather.

(7) The flame retardant performance of suede-like artificial leather is classified into Category 3 in the flammability test method JIS L 1091 A-2 method (45 ° Meckel burner method) of textile products, and JIS L 1091 D method (coil) The suede-like artificial leather excellent in flame retardancy according to any one of the above (1) to (6), wherein the number of times of flame contact is 4 or more.

(8) The light fastness on the front side and back side of the suede-like artificial leather is the dyeing fastness test method JIS L 0842 for ultraviolet carbon arc lamp light. The suede-like artificial leather excellent in flame retardancy according to any one of the above (1) to (7), which has a grade 4-5 or higher in gray scale determination for fading.

  Moreover, the manufacturing method of the suede tone artificial leather excellent in the flame retardance of this invention which achieves the objective mentioned above has the structure of the following (9).

(9) A method for producing a suede-like artificial leather excellent in flame retardancy as described in any one of (1) to (8) above, wherein the fabric has raised surfaces and is impregnated with a polyurethane resin Production of suede-like artificial leather excellent in flame retardancy, characterized by performing the following steps (a), (b), and (c) on a thermoplastic synthetic fiber fabric comprising a knitted fabric or a non-woven fabric Method.
(A) Step of providing a flame retardant compound A containing phosphorus or nitrogen atom (b) Aqueous dispersion of ammonium polyphosphate, phosphoric ester, fluorine-based water repellent, light resistance improver and polyester resin on one side Step (c) of applying a flame retardant composition B comprising a binder resin is an upper layer of the flame retardant composition B, from a binder resin that is an aqueous dispersion of the same polyester resin used in the step (b). A step of applying a protective layer

  According to the present invention, it is a flame retardant suede-like artificial leather that is excellent in flame retardancy and light resistance, hardly causes sticking, and does not easily scratch the application surface of the flame retardant composition, and uses a halogen-based flame retardant. There are not provided so-called flame retardant suede-like artificial leather treated with a non-halogen flame retardant and a method for producing the same.

  Hereinafter, the suede-like artificial leather of the present invention and the manufacturing method thereof will be described in more detail.

The suede-like artificial leather, which is a constituent element of the suede-like artificial leather excellent in flame retardancy according to the present invention, is a suede-like texture comprising a woven fabric, a knitted fabric, or a non-woven fabric having raised or raised nap on the surface and impregnated with a polyurethane resin. Is known as suede artificial leather using ultrafine thermoplastic synthetic fibers (generally 0.0001-1.1 dtex ultrafine fibers) and polyurethane resin. The artificial leather of the present invention is a suede-like artificial leather having a basis weight of 450 g / m ² or more, and is provided with a flame retardant compound A containing phosphorus or nitrogen atoms, On one side, a binder resin that is an aqueous dispersion of ammonium polyphosphate, phosphate ester, fluorine-based water repellent, light resistance improver, and polyester resin And a protective layer made of a binder resin, which is an aqueous dispersion of the polyester resin, is applied to the upper layer of the applied flame retardant composition B. Suede-like artificial leather with excellent flame retardancy.

  Further, the method for producing a suede-like artificial leather excellent in flame retardancy according to the present invention imparts excellent flame-retardant performance to the suede-like artificial leather. This processing step is performed.

  The first step (a) is a step of imparting a flame retardant compound A containing phosphorus or nitrogen atoms to the suede-like artificial leather.

  In the second step (b), a flame retardant composition B composed of ammonium polyphosphate, phosphate ester, fluorine-based water repellent, light resistance improver and binder resin is applied to one surface of the suede-like artificial leather. It is a process of giving.

  The third stage processing step (c) is a step of applying a protective layer made of the binder resin used in the second stage processing step to the upper layer of the flame retardant composition B applied to one side of the suede-like artificial leather. It is.

  More detailed explanation will be given below.

  In the method of the present invention described above, the first stage processing step is a step of applying the flame retardant compound A to the suede-like artificial leather. The purpose is to assist the flame retardant performance of the flame retardant composition B applied to one side of the suede-like artificial leather in the second step. From the viewpoint that the texture, touch, and surface appearance of the suede-like artificial leather are impaired when the applied amount is too large, the applied amount of the flame retardant compound A is preferably 100 parts by weight of the fabric (including polyurethane). It is good to set it in the range of 1-10 weight part, More preferably, it is in the range of 2-8 weight part. When the applied amount is 1 part by weight or less with respect to 100 parts by weight of the fabric, the flame retardancy assisting effect is weak, and when it exceeds 10 parts by weight, the texture, touch, and surface appearance of the suede-like artificial leather are impaired and difficult. There are concerns such as a decrease in fastness to surface friction due to the flammable compound A and a bleed out of the drug over time (a phenomenon in which a part of the composition in the composition exudes to the surface of the molded product).

ここで、Ｘ；０，１ As the flame retardant compound A, a compound containing phosphorus or a nitrogen atom is used, and more preferable specific examples include guanidine phosphate, guanidine sulfamate and a cyclic phosphonic acid represented by the following general formula [1]. At least one or two or more of the esters are used.

Where X; 0, 1

  The application method of the flame retardant compound A is not particularly limited, and either a spray method or a padding method can be employed. As the spraying method, an aqueous liquid containing the flame retardant compound A is applied to one or both sides of the suede-like artificial leather with a spray nozzle so as to have a predetermined adhesion amount, and is 100 to 130 ° C. A method of drying for 1 to 10 minutes can be employed. Moreover, as a padding method, a suede-like artificial leather is immersed in an aqueous liquid containing the flame retardant compound A, and is squeezed to a predetermined adhesion amount with a mangle or the like, and is 100 to 130 ° C. for 1 to 10 minutes. A drying method can be adopted.

  The second stage processing step is a step of applying a flame retardant composition B composed of ammonium polyphosphate, phosphoric ester, fluorine-based water repellent, light resistance improver and polyester resin to one side of the suede-like artificial leather. The flame retardant composition B is preferably applied to the back surface (that is, the surface having no napping).

  The main flame retardant mechanism of the flame retardant composition B is the action of flame retardant by the carbonization / dehydration reaction of ammonium polyphosphate, but the purpose of using the phosphate ester is the flame retardant auxiliary action by the drip effect, Thereby, the flame retardancy which suits JIS L 1091 A-2 method division 3 can be achieved.

（ただし、式中ｎは、ポリ燐酸アンモニウムの重合度を表し、その値は通常１〜５，０００、好ましくは３〜２，０００、特に好ましくは５〜１，０００である。） The ammonium polyphosphate of the present invention is a compound represented by the following general formula [3], and a branched one or one in which a terminal is partially substituted with another group can also be used. More desirably, the compound has a phosphorus content of about 25 to 32% by weight.

(In the formula, n represents the degree of polymerization of ammonium polyphosphate, and the value is usually 1 to 5,000, preferably 3 to 2,000, and particularly preferably 5 to 1,000.)

  As the phosphoric acid ester, an oil-based phosphoric acid ester such as triphenyl phosphate or resorcinol bisdiphenyl phosphate can provide a flame retardant auxiliary effect, but in the present invention, bisphenol A bisdiphenyl phosphate having excellent hydrolysis resistance may be used. preferable.

The fluorine-based water repellent can prevent sticking when used in combination with the polyester resin. Even if a paraffinic or higher fatty acid amide water repellent is used, the effect cannot be obtained. The fluorine-based water repellent is an acrylic copolymer containing a perfluoroalkyl group or a perfluoroalkenyl group and has no problem in compatibility with the polyester resin, and is not particularly limited. However, a water / oil repellent composition containing a polymer of (meth) acrylate having an R ^f group shown below is preferred. [(Meth) acrylate is a generic term for acrylate and methacrylate. ]

The R ^f group is a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. 2-20 are preferable and, as for carbon number of ^Rf group, 6-16 are especially preferable. The R ^f group may have a linear structure or a branched structure, and a linear structure is particularly preferred. In the case of a branched structure, the branched portion is preferably present at the terminal portion of the R ^f group and is a short chain having about 1 to 4 carbon atoms. The R ^f group must not contain a halogen atom other than a fluorine atom. Further, an etheric oxygen atom or a thioetheric sulfur atom may be inserted between the carbon-carbon bonds in the R ^f group. Examples of the structure of the terminal portion of the R ^f group include —CF ₂ CF ₃ , —CF (CF ₃ ) ₂ , —CF ₂ H, —CFH _{2 and the} like, and —CF ₂ CF ₃ is preferable.

The number of fluorine atoms in the R ^f group is [(number of fluorine atoms in the R ^f group) / (number of hydrogen atoms contained in the corresponding alkyl group having the same carbon number as the R ^f group)] × 100 (%). In terms of expression, 60% or more is preferable, and 80% or more is particularly preferable. Furthermore, since the R ^f group is excellent in preventing sticking when used in combination with a polyester resin, a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (that is, a perfluoroalkyl group) is preferable. 2-20 are preferable and, as for carbon number of a perfluoroalkyl group, 6-16 are especially preferable. Specific examples of the R ^f group include
_{C 4 F 9 - [F (} CF 2) 4 -, (CF 3) 2 CFCF 2 -, (CF 3) 3 C-, or any _{CF 3 CF 2 (CF 3)} CF- structurally isomeric groups such _or], C _{5 F 11} - [e.g. _{F (CF 2) 5 -]} , C 6 F 13 - [ e.g. _{F (CF 2) 6 -]} , C 7 F 15 - [ e.g. _{F (CF 2)} 7 -] , _C 8 _{F 17} - [e.g. _{F (CF 2) 8 -]} , C 9 F 19 - [ e.g. _{F (CF 2) 9 -]} , C 10 F 21 - [ e.g. _{F (CF 2) 10 -]} , C ₁₂ F ₂₅ - [e.g. _{F (CF 2) 12 -]} , C 14 F 29 - [ e.g. _{F (CF 2) 14 -]} , C 16 F 33 - [ e.g. _{F (CF 2) 16 -]} , H (CF _{2) t} - [wherein, t is an integer of _{2~20], (CF 3) 2} CF (CF 2) y - [ In this, y is an integer of _{1~17], F (CF 2)} 5 OCF (CF 3) -, F [CF (CF 3) CF 2 O] r CF (CF 3) CF 2 CF 2 -, F [ _{CF (CF 3) CF 2 O} ] u CF (CF 3) -, F [CF (CF 3) CF 2 O] u CF 2 CF 2 -, F [CF 2 CF 2 CF 2 O] u CF 2 CF 2 _{-, F [CF 2 CF 2} O] u CF 2 CF 2 -, F (CF 2) 5 SCF (CF 3) -, F [CF (CF 3) CF 2 S] r CF (CF 3) CF 2 CF _{2 -, F [CF (CF} 3) CF 2 S] u CF (CF 3) -, F [CF (CF 3) CF 2 S] u CF 2 CF 2 -, F (CF 2 CF 2 CF 2 S) _{w CF 2 CF 2 -, F} (CF 2 CF 2 S) w CF 2 CF 2 - (r is an integer of from 1 to 5, u Is an integer of 1 to 6, and w is an integer of 1 to 9).

As the (meth) acrylic acid ester constituting the polymer of (meth) acrylate having an R ^f group, a compound represented by the following general formula [4] is preferable.
General formula [4]
R ^f -Q-OCOCR = CH ₂
(Q represents a divalent organic machine, and R represents a hydrogen atom or a methyl group.)

As Q in the general formula _{[4], - (CH 2} ) p + q -, - (CH 2) p O (CH 2) q -, - CF = CH (CH 2) p -, - (CH 2) p _{CONH (CH 2) q -,} - (CH 2) p OCONH (CH 2) q -, - (CH 2) p SO 2 NR' (CH 2) q -, - (CH2) pNHCONH (CH2) q-, _{- (CH 2) p CH (} OH) - (CH 2) q -, etc. are preferable. Here, R ′ represents a hydrogen atom or an alkyl group. Moreover, p and q show an integer greater than or equal to 0, and p + q is an integer of 1-22. Among these, Q is _{- (CH 2) p + q} -, - (CH 2) p CONH (CH 2) q -, or _{(CH 2) p SO 2 NR'} (CH 2) q - and may, and q is It is preferably an integer of 2 or more, and p + q is preferably 2 to 6, particularly — (CH ₂ ) _{p + q} — (that is, ethylene group, trimethylene group, tetramethylene group, heptamethylene group or p + q is 2 to 6 or Hexamethylene group) is preferred. In the general formula [4], a fluorine atom is preferably bonded to the carbon atom of R ^f bonded to Q.

Specific examples of the (meth) acrylic acid ester constituting the (meth) acrylate polymer having an R ^f group include the following compounds.

CF ₃ (CF ₂ ) ₄ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCR═CH ₂
CF ₂ H (CF ₂ ) ₅ CH ₂ OCOCR═CH ₂
CF ₂ H (CF ₂ ) ₇ CH ₂ OCOCR═CH ₂
CF ₂ H (CF ₂ ) ₉ CH ₂ OCOCR═CH ₂
CF ₂ H (CF ₂ ) ₇ CH ₂ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₁₃ CH ₂ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₁₅ CH ₂ CH ₂ OCOCR═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCR═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR═CH _{2
CF 3 (CF 2) 7 SO} 2 N (C 3 H 7) CH 2 CH 2 OCOCR = CH 2
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ CH ₂ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₇ CONHCH ₂ CH ₂ OCOCR═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH ₂ CH ₂ OCOCR═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OCOCH ₃ ) OCR═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ OCOCR═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR═CH ₂
CF ₃ (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOCR═CH ₂
(Here, R represents a hydrogen atom or a methyl group.)

The (meth) acrylic acid ester constituting the polymer of (meth) acrylate having these R ^f groups may be polymerized alone or in combination of two or more.

  Further, the fluorine-based water repellent that can be used in the present invention is based on homopolymerization of only a vinyl monomer having a polyfluoroalkyl group or a polyfluoroalkenyl group represented by the general formula [4], Examples include those obtained by copolymerization of these vinyl monomers with other vinyl monomers having no polyfluoroalkyl group or polyfluoroalkenyl group.

Examples of other vinyl monomers having no polyfluoroalkyl group or polyfluoroalkenyl group include (meth) acrylic acid alkyl esters having 1 to 20 carbon atoms in the alkyl group part, olefin, vinyl carboxylate, and styrene. And substituted styrene, acrylamide and methacrylamide, N-substituted acrylamide and N-substituted methacrylamide, vinyl alkyl ether, (substituted alkyl) vinyl ether, vinyl alkyl ketone, diene, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, substituted alkyl (Meth) acrylate, hydroxyalkyl (meth) acrylate, hydroxyl-terminated polyoxyalkylene (meth) acrylate, alkoxy-terminated polyoxyalkylene (meth) acrylate, polyoxyal Range (meth) acrylate, polysiloxane group-containing (meth) acrylate, triallyl cyanurate, allyl glycidyl ether, allyl carboxylate, N-vinylcarbazole, N-methylmaleimide, maleic anhydride, monoalkyl maleate, maleic acid Examples include dialkyl esters and blocked isocyanate group-containing (meth) acrylates. These may be copolymerized alone with the (meth) acrylic acid ester constituting the polymer of (meth) acrylate having an R ^f group, or two or more kinds may be used in combination.

  Specific examples of water repellents that can be used in the present invention include Asahi Guard AG-950 and Asahi Guard AG-7000 manufactured by Asahi Glass Co., Ltd., Paraguard EC-95 and Paraguard EC-450 manufactured by Ohara Palladium Chemical Co., Ltd. However, it is not particularly limited.

  The light resistance improver is used to improve the light resistance of the suede-like artificial leather. Light resistance can be improved with benzoate UV absorbers and hindered amine light stabilizers, but at least one selected from benzotriazole UV absorbers and semicarbazide light stabilizers can be used. Particularly excellent light resistance can be obtained.

  Accordingly, in the present invention, the light resistance improver is preferably a benzotriazole-based ultraviolet absorber or a semicarbazide-based light stabilizer.

  Specific examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole and 2- (2-benzotriazol-2-yl)-. 4,2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2) -Yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 3- (2H-benzotriazol-2-yl) -5- ( 1,1-dimethylethyl) -4-hydroxy-octyl ester.

（ただし、式中Ｒ_１ 〜Ｒ_４ は同一もしくは異なるＣ_１ 〜Ｃ_４ のアルキル基を示し、Ｘは炭素数１５以下の２価の炭化水素基を示す。） Moreover, as a semicarbazide type | system | group, it is a compound represented by following General formula [2], Comprising: As a specific example, 1, 6-hexamethylene bis (N, N- dimethyl semicarbazide), 4, 4'- ( Methylenedi-p-phenylene) bis (N, N-diethylsemicarbazide), 4,4 ′-(methylenedi-p-phenylene) bis (N, N-di-i-propylsemicarbazide), α, α- (p-xylylene) ) Bis (N, N-dimethylsemicarbazide), 1,4-cyclohexylenebis (N, N-dimethylsemicarbazide) and the like.

(Wherein, R _{1 to} R ₄ represent the same or different C _{1 to} C ₄ alkyl groups, and X represents a divalent hydrocarbon group having 15 or less carbon atoms.)

  These compounds may be used alone or in combination of two or more.

  In the present invention, the use of a polyester resin as a binder component in the flame retardant composition B has a purpose and a stickiness for promoting dripping of resin melt (also referred to as drip) during combustion with a phosphoric ester. The purpose is to make it difficult. The greater the amount of the polyester resin used in the present invention, the more stable the flame retardancy and the less likely it will be.

  The binder resin used in the present invention promotes the drip effect, hardly causes sticking, and is compatible with ammonium polyphosphate, phosphate ester, light resistance improver, and fluorine-based water repellent used in the present invention. If there is no problem, there is no particular limitation.

  The polyester resin used in the present invention uses an aqueous dispersion of a polyester resin. The polyester resin as a solid content is a polymer compound composed of an acid component and an alcohol component, but is used during polymerization. The acid component contains sulfophthalic acids and aliphatic dicarboxylic acids, and the alcohol component contains aliphatic polyhydric alcohols.

  Examples of the sulfophthalic acids include sodium 3-sulfoterephthalate and alkyl esters such as methyl, ethyl, and propyl esters thereof, ethylene glycol esters, sodium 5-sulfoisophthalate and alkyl esters such as methyl, ethyl, and propyl esters, and ethylene. A glycol ester etc. are mentioned. Examples of the aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Examples of aliphatic polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. Diol, 1,8-octanediol, 1,10-dodecanediol, neopentyl glycol, dimethylol heptane, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol, polypropylene glycol And aliphatic diols such as polytetramethylene glycol, triols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, and tetraols.

  Such a polyester resin aqueous dispersion may be used alone or in combination of two or more. In addition, as long as the flame retardancy and the anti-sticking effect are not impaired, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and fats such as 1,4-cyclohexanedicarboxylic acid are used as acid components. 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, spiroglycol, hydrogenated bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, tricyclodecane as cyclic dicarboxylic acids and alcohol components Ethylene oxide addition of alicyclic polyhydric alcohols such as diol and tricyclodecane dimethanol, para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol and 1,4-phenylene glycol , It may also contain an aromatic polyhydric alcohol such as bisphenol A, ethylene oxide adduct of bisphenol A and propylene oxide adducts.

  In addition, an additive such as an antistatic agent or a crosslinking agent is added to the flame retardant composition B within a range in which flame retardancy, light resistance, stickiness, and stability of processing chemicals are not inhibited. Can do.

  As an application amount of the above-mentioned flame retardant composition B, ammonium polyphosphate is preferably 5 to 20 parts by weight, more preferably 8 to 15 parts by weight with respect to 100 parts by weight of the dough. If it is less than 5 parts by weight, the flame retardancy is insufficient, and if it exceeds 20 parts by weight, the stickiness and light resistance are impaired.

  The application amount of the phosphate ester is preferably 0.3 to 4 parts by weight, more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the dough. When the applied amount is less than 0.3 parts by weight, the drip effect is weak and the flame retardancy is insufficient. When the applied amount exceeds 4 parts by weight, there is a risk that the stickiness is deteriorated or the daily bleed out is caused. is there.

  The amount of the fluorine-based water repellent applied is preferably 0.1 to 1.5 parts by weight, more preferably 0.3 to 1.0 parts by weight with respect to 100 parts by weight of the fabric. When the applied amount is less than 0.1 parts by weight, the suppression of sticking is insufficient, and when it exceeds 1.5 parts by weight, the flame retardancy may be hindered, and the water repellent effect becomes remarkable. When the water droplets adhere to the surface, the water droplets dries on the fiber surface as water droplets, so that water-soluble components gather around the water droplets and cause a sticking phenomenon.

  The application amount of the light resistance improver is preferably 0.1 to 1.5 parts by weight, more preferably 0.3 to 1.0 parts by weight with respect to 100 parts by weight of the dough. If the applied amount is less than 0.1 parts by weight, the light resistance is insufficient, and if it exceeds 1.5 parts by weight, the benzotriazole type cannot be used because the hue is whitened, and the semicarbazide type has a prominent May cause this.

  The amount of the binder resin applied is preferably 2 to 10 parts by weight, more preferably 4 to 8 parts by weight with respect to 100 parts by weight of the dough. When the applied amount is less than 2 parts by weight, the flame retardant component is not sufficiently fixed to the fiber and the sticking tends to occur, and the stability of the flame retardant performance is insufficient. The balance of is lost, and the flame retardancy is reduced.

  The application method of the flame retardant composition B is not particularly limited, and either a rotary screen processing method or a comma coater can be employed. As a rotary screen processing method, the flame retardant composition B is adhered to one side of a suede-like artificial leather so as to have a predetermined adhesion amount using a rotary screen, and dried at 100 to 130 ° C. for 1 to 10 minutes. The method to do can be adopted. Further, as a comma coater method, the flame retardant composition B is adhered to one side of a suede-like artificial leather so as to have a predetermined adhesion amount by using a comma coater, and is performed at 100 to 130 ° C. for 1 to 10 minutes. A drying method can be adopted.

  The third stage processing step (c) is a step for further improving the performance, and a protective layer is formed on the flame retardant composition B provided on one side of the suede-like artificial leather in the second stage processing step. As a step of applying a polyester resin. By providing the protective layer, the surface of the flame retardant composition can be made less likely to be scratched, and the stickiness can be further improved.

  As the resin layer used for the protective layer, it is important to use the same binder resin as the constituent element in the flame retardant composition B applied in the second processing step (b). If the binder resin used in the second stage processing step and the resin applied in the third stage are different resins, the flame retardancy may be reduced.

  Further, in the third processing step, the protective layer has a flame retardant, a light resistance improver, a water repellent, an antistatic agent, and a crosslinking agent within a range in which flame retardancy, light resistance and stickiness are not inhibited. Etc. can be mix | blended.

  The amount of resin applied in the third stage processing step is preferably 1.5 with respect to 100 parts by weight of artificial leather (including the compounds and resin compositions applied in the first and second stage processing steps). -8 parts by weight, more preferably 2-5 parts by weight. If the amount is less than 1.5 parts by weight, the surface of the flame retardant composition processed in the second stage is insufficiently protected and easily damaged. If the amount exceeds 8 parts by weight, the thickness of the protective layer increases. The balance of flame retardancy will be lost.

  The method for applying the binder resin as the protective layer is not particularly limited, and either a rotary screen processing method or a comma coater processing method can be employed. As the rotary screen processing method, a polyester resin is applied using a rotary screen as a protective layer of the flame retardant composition B, and preferably, for example, a method of drying at 100 to 130 ° C. for 1 to 10 minutes is adopted. can do. Further, as the comma coater processing method, a binder resin is applied using a comma coater as a protective layer of the flame retardant composition B, and preferably dried at 100 to 130 ° C. for 1 to 10 minutes, for example. Can be adopted.

Moreover, it is important that the weight of the suede-like artificial leather excellent in flame retardancy of the present invention is 450 g / m ² or more. If the basis weight is less than 450 g / m ² , the evaluation method of flame retardancy is JIS L 1091 A-1 method (45 ° micro burner method), the behavior during combustion changes, and it may not be able to conform to Category 3. is there. The upper limit of the basis weight is up to about 600 g / m ² . The suede-like artificial leather according to the present invention is intended for use as an interior material, and if the basis weight is larger than that, from the viewpoint of use, problems such as deterioration of texture, cost increase, and further from the processing surface Has a problem that it is difficult to adhere, and is not common.

  The suede-like artificial leather having excellent flame retardancy according to the present invention is obtained by subjecting the artificial leather base fabric impregnated and raised with a polymer elastic body to a dyeing treatment, and then processing the first to third stages. Can be obtained.

  As the artificial leather base fabric, a fabric, knitted fabric or nonwoven fabric containing synthetic fibers having a single fiber fineness of 1 dtex or less is impregnated with a polymer elastic body. Preferably, the synthetic fiber contains 0.5 decitex or less, more preferably 0.3 decitex or less. And it is preferable that a woven fabric, a knitted fabric, or a nonwoven fabric has napping. Synthetic fibers used here include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate and polyester-based synthetic fibers typified by copolyester fibers based on these, nylon 6 and nylon 6,6. Synthetic fibers such as representative polyamide-based synthetic fibers and polypropylene-based fibers can be used. Among these, polyethylene terephthalate fibers excellent in dyeability, dyeing fastness and abrasion resistance are preferable.

  The manufacturing method of the artificial leather base fabric in the present invention is not particularly limited, and a normal method can be used. For example, a composite fiber containing polystyrene as a sea component and polyester as an island component is spun by the sea-island spinning method, and the composite fiber is used to fabricate a fiber by a spun bond, a melt blow, a paper making method, a method in which a card and a cross wrapper are combined, or the like. A web is formed, and an entangled nonwoven fabric is formed using the fiber web by an entanglement process such as a needle punch process or a water jet punch process. In addition, about this entanglement process, a needle punch process is preferably employ | adopted from a viewpoint of the densification of fiber (dense raised surface formation) by the high entanglement of a fiber.

  Next, the sea component of the composite fiber is removed by a method such as solvent extraction or thermal decomposition. At that time, a method of solvent extraction before or after the polymer elastic body is applied is preferably employed from the viewpoint of the sea component removal rate. As the polymer elastic body, polyurethane elastomer, acrylonitrile, butadiene rubber, natural rubber or the like can be used. Further, as a method for applying the polymer elastic body, a method of applying or impregnating the polymer elastic body and drying and fixing it can be employed.

  Subsequently, an artificial leather base fabric having a raised surface can be obtained by subjecting the non-woven fabric provided with the polymer elastic body to a raising process using sandpaper or the like.

  In this invention, it does not specifically limit as a method to dye | stain with respect to the said artificial leather, A normal method can be used. For example, liquid dyeing using a jaguar dyeing machine or liquid dyeing machine, immersion dyeing such as thermosol dyeing using a continuous dyeing machine, and surface raising by roller printing, screen printing, inkjet printing, sublimation printing, etc. Can be used. Among these, it is preferable to use a liquid dyeing machine from the viewpoint of quality such as texture. Moreover, you may give a resin finishing process after dyeing | staining as needed.

  The suede-like artificial leather of the present invention produced as described above has excellent flame retardancy.

  In particular, according to the knowledge of the present inventors, 1 to 10 parts by weight of flame retardant compound A in the second stage of processing step in the first stage of processing step with respect to 100 parts by weight of the fabric (including polyurethane). As the flame retardant composition B component, 5 to 20 parts by weight of ammonium polyphosphate, 0.3 to 4 parts by weight of phosphate ester, and 2 to 10 parts by weight of binder resin (polyester resin aqueous dispersion) are added. The flame-retardant suede-like artificial leather manufactured by the present invention achieves Category 3 in the measurement by the flammability test method JIS L 1091 A-2 method (45 ° Meckel burner method) of textile products. Can do. Further, in the measurement by the JIS L 1091 D method (coil method), the number of flame contact can be 4 times or more. Further, as a protective layer, in the third processing step, the binder resin (polyester resin aqueous dispersion) is added to 1.5 to 8 parts by weight with respect to 100 parts by weight of the fabric (including polyurethane). Flame performance can be achieved.

  Moreover, in addition to the above, in the second processing step, a benzotriazole-based or semicarbazide-based light resistance improver is added as 0.1 to 100 parts by weight of the fabric (including polyurethane) as the flame retardant composition B component. The suede-like artificial leather excellent in flame retardancy of the present invention produced by adding ~ 1.5 parts by weight has excellent light resistance, and the surface of the suede-like artificial leather When the light fastness is measured by the dyeing fastness test method JIS L 0842 5th exposure method (under 63 ± 3 ° C., 40 hours exposure) with respect to both sides of the side and the back side, both surfaces change. Grade 4-5 or higher can be achieved by gray scale determination for fading. By the way, even if the conventional suede-like artificial leather has excellent weather resistance only on one side, the other side does not have weather resistance or it is almost inferior, The suede-like artificial leather of the present invention has a front surface and a back surface each having a grade 4-5 or higher.

  Furthermore, in addition to the above, 0.1 to 1.5 parts by weight of a fluorine-based water repellent as a flame retardant composition B component in 100 parts by weight of the fabric (including polyurethane) in the second stage processing step The suede-like artificial leather excellent in flame retardancy of the present invention produced by imparting is less likely to cause sticking, and can achieve the flame retardancy and light resistance as described above.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Moreover, the quality evaluation in an Example was implemented with the following method.

(1) Flammability test 1999 version JIS L 1091 A-2 method (45 ° Meckel burner method) and JIS L 1091 D method (coil method) were evaluated.
(2) Stickiness The cross section of the test sample was immersed in water by 5 mm, allowed to stand for 5 hours, and then the state of the sample after natural drying was observed.
(3) Light resistance In 2004 JIS L 0842 5th exposure method, it measured by exposure for 40 hours under 63 +/- 3 degreeC from the surface side and the back surface side.
(4) Chalk mark The ease of scratching was observed when the surface of the binder resin as a protective layer was rubbed with a nail. Judgment was made based on whether the scratches were noticeable or not.

In Examples 1 to 6 and Comparative Examples 1 to 8, a suede-like artificial leather base fabric having a basis weight of 375 g / m ² and a comparative example 9 having a basis weight of 130 g / m ² was used. All the samples used for the test were provided with a flame retardant compound A, a flame retardant composition B, and a polyester resin as a protective layer by the following treatment method.

  The flame retardant compound A was treated by a padding method and dried at 100 ° C. for 10 minutes.

  The flame retardant composition B was treated with a comma coater and dried at 100 ° C. for 10 minutes.

  The binder resin as the protective layer was treated with a comma coater and dried at 100 ° C. for 10 minutes.

Example 1
Guanidine phosphate is used as the flame retardant composition A, the phosphoric acid ester which is a constituent of the flame retardant composition B is bisphenol A bisdiphenyl phosphate, and the water repellent is fluorine-based (Asahi Guard AG manufactured by Asahi Glass Co., Ltd.). -950), 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-octyl ester for light resistance improver, and polyester resin aqueous dispersion for binder resin. Using this polyester resin aqueous dispersion as a protective layer, a suede-like artificial leather having a basis weight of about 499 g / m ² was obtained.
As the polyester resin aqueous dispersion, one synthesized by the following method was used.
In a 1-liter flask equipped with a stirrer, a thermometer, a rectifying column and an inert gas introduction tube, 155.2 g of dimethyl terephthalic acid, 23.0 g of dimethyl sebacic acid, 29.6 g of dimethyl sodium 5-sulfoisophthalate, ethylene glycol 136.0 g, polyethylene glycol (number average molecular weight 4000) 600.0 g, manganese acetate tetrahydrate 0.2 g as a transesterification catalyst and tetrabutyl titanate 0.1 g as a polycondensation catalyst were charged, and transesterification was performed at 150 to 250 ° C. Reaction was performed. When the internal temperature reached 150 ° C., methanol began to distill, and when the internal temperature was gradually increased to 250 ° C., the transesterification reaction was completed. Subsequently, 0.2 g of trimethyl phosphate was added, the internal temperature was lowered to 200 ° C., and a polycondensation reaction was carried out for 1 hour under a reduced pressure of 10 mmHg to obtain a polyester resin having a number average molecular weight of 15000. Further, 3500 g of hot water at 50 ° C. was put into a 10 liter beaker, and while stirring with a homogenizer, 618 g of the polyester resin having the number average molecular weight of 15000 cooled to 180 ° C. was slowly dropped and dispersed for 30 minutes. Upon cooling, an aqueous dispersion of a polyester resin having a solid content of 15% was obtained.

Example 2
A suede-like artificial leather having a basis weight of about 499 g / m ² was obtained in the same manner as in Example 1 except that 1,6-hexamethylenebis (N, N-dimethylsemicarbazide) was used as the light resistance improver.

Example 3
A suede-like artificial leather having a basis weight of about 499 g / m ² was obtained in the same manner as in Example 1 except that guanidine sulfamate was used for the flame retardant composition A.

Example 4
A suede-like artificial leather having a basis weight of about 484 g / m ² was obtained in the same manner as in Example 1 except that a cyclic phosphonic acid ester was used for the flame retardant composition A.

Example 5
Except for using 2,4-di-tertiarybutylphenyl-3,5-di-tertiarybutyl-4-hydroxybenzoate as the light fastness improver, the basis weight was about 499 g / m ^{2 in} the same manner as in Example 1. Suede-like artificial leather was obtained.

Example 6
Except for using bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate as a light fastness improver, a suede-like artificial leather having a basis weight of about 499 g / m ² was obtained in the same manner as in Example 1. .

Comparative Example 1
A suede-like artificial leather having a basis weight of about 499 g / m ² was obtained in the same manner as in Example 1 except that triphenyl phosphate was used as the phosphate ester.

Comparative Example 2
A suede-like artificial leather having a basis weight of about 499 g / m ² was obtained in the same manner as in Example 1 except that resorcinol bisdiphenyl phosphate was used as the phosphate ester.

Comparative Example 3
A suede-like artificial leather having a basis weight of about 499 g / m ² was obtained in the same manner as in Example 1 except that a paraffin type (Paragit PR New manufactured by Meisei Chemical Industry Co., Ltd.) was used as the water repellent.

Comparative Example 4
A suede-like artificial leather having a basis weight of about 499 g / m ² was obtained in the same manner as in Example 1 except that a higher fatty acid amide system (Maisei Chemical Co., Ltd. Uniperan PA) was used as the water repellent.

Comparative Example 5
A suede-like artificial fabric having a basis weight of about 499 g / m ² was used in the same manner as in Example 1 except that a polyurethane resin aqueous dispersion (Dainippon Ink & Chemicals Co., Ltd. Hydran WLS-210) was used for the binder resin and the protective layer. Got leather.

Comparative Example 6
Except for using an acrylic ester resin aqueous dispersion (Dai Nippon Ink Chemical Co., Ltd. Boncoat AB-782-E) for the binder resin and the protective layer, the basis weight was approximately 499 g / m ^{2 in the same} manner as in Example 1. Of suede-like artificial leather.

Comparative Example 7
A suede-like artificial leather having a basis weight of about 499 g / m ² was obtained in the same manner as in Example 1 except that a polyurethane resin aqueous dispersion (Dainippon Ink & Chemicals Co., Ltd. Hydran WLS-210) was used for the protective layer. It was.

Comparative Example 8
A suede tone having a basis weight of about 499 g / m ² is the same as in Example 1 except that an acrylic ester resin aqueous dispersion (Dai Nippon Ink Chemical Co., Ltd. Boncoat AB-782-E) is used as the binder resin. An artificial leather was obtained.

Comparative Example 9
A suede-like artificial leather having a basis weight of about 173 g / m ² was obtained in the same manner as in Example 1 except that a suede-like artificial leather base fabric having a basis weight of 130 g / m ² was used.

  The details and evaluation results of the suede-like artificial leathers obtained in Examples 1 to 6 and Comparative Examples 1 to 9 are shown in Tables 1 and 2, respectively.

  From Table 1 and Table 2, the present invention has good flame retardancy without using a halogen-based flame retardant, and is excellent in light fastness on both the front and back sides of the fabric, It can be seen that the fabric is a suede-like artificial leather having excellent flame retardancy, in which the surface side and the back side of the fabric are less likely to have sticking, and the coated surface of the flame retardant composition is hardly scratched.

Claims (9)

It is a suede-like artificial leather having a basis weight of 450 g / m ² or more, provided with a flame retardant compound A containing phosphorus or nitrogen atoms, and further, on one side, ammonium polyphosphate, phosphate, fluorine A flame retardant composition B comprising a water-repellent agent, a light resistance improver, and a binder resin which is an aqueous dispersion of a polyester resin, and the polyester resin is provided on the flame retardant composition B provided A suede-like artificial leather excellent in flame retardancy, which is provided with a protective layer made of a binder resin which is an aqueous dispersion of the above. 2. The flame retardant compound A contains at least one selected from the group consisting of guanidine phosphate, guanidine sulfamate, and a cyclic phosphonate represented by the following general formula [1]. Suede-like artificial leather with excellent flame resistance.

Where X; 0, 1   The suede-like artificial leather excellent in flame retardancy according to claim 1 or 2, wherein the phosphate ester is bisphenol A bisdiphenyl phosphate.   The suede-like artificial leather excellent in flame retardancy according to any one of claims 1 to 3, wherein the fluorine-based water repellent is a perfluoroalkyl group- or perfluoroalkenyl group-containing acrylic copolymer.   5. The flame retardant according to claim 1, wherein the light resistance improver contains at least one selected from a benzotriazole-based ultraviolet absorber and a semicarbazide-based light stabilizer. Suede artificial leather.   In the binder resin which is an aqueous dispersion of a polyester resin, the polyester resin which is a solid content is a polymer compound composed of an acid component and an alcohol component. The suede-like artificial leather excellent in flame retardancy according to any one of claims 1 to 5, comprising dicarboxylic acid as an alcohol component and aliphatic polyhydric alcohol.   The flame retardant performance of suede-like artificial leather is classified into Category 3 in the flammability test method JIS L 1091 A-2 method (45 ° Meckel burner method) of textile products, and in the JIS L 1091 D method (coil method) The suede-like artificial leather excellent in flame retardancy according to any one of claims 1 to 6, wherein the number of flame contacts is 4 or more.   The light fastness of the front and back sides of the suede-like artificial leather is discolored when exposed to light at 63 ± 3 ° C. for 40 hours in the JIS L 0842 Fifth Exposure Method for dyeing fastness to ultraviolet carbon arc lamp light. The suede-like artificial leather excellent in flame retardancy according to any one of claims 1 to 7, which has a grade 4-5 or higher in gray scale determination for use. A method for producing a suede-like artificial leather excellent in flame retardancy according to any one of claims 1 to 8, comprising a woven fabric, a knitted fabric or a non-woven fabric having raised surfaces and impregnated with a polyurethane resin. A method for producing a suede-like artificial leather excellent in flame retardancy, wherein the thermoplastic synthetic fiber fabric is subjected to the following steps (a), (b) and (c):
(A) Step of providing a flame retardant compound A containing phosphorus or nitrogen atom (b) Aqueous dispersion of ammonium polyphosphate, phosphoric ester, fluorine-based water repellent, light resistance improver and polyester resin on one side Step (c) of applying a flame retardant composition B comprising a binder resin is an upper layer of the flame retardant composition B, from a binder resin that is an aqueous dispersion of the same polyester resin used in the step (b). A step of applying a protective layer