TWI772186B - Polyolefin synthetic fiber nonwoven fabric treatment agent, polyolefin synthetic fiber, and polyolefin synthetic fiber spunbonded nonwoven fabric - Google Patents

Abstract

The subject to be solved by the present invention is to improve the wettability of the treatment agent for a polyolefin-based synthetic fiber nonwoven fabric and to improve the durable hydrophilicity of the polyolefin-based synthetic fiber spunbond nonwoven fabric. The treating agent for nonwoven fabrics made of polyolefin-based synthetic fibers of the present invention is characterized by containing a specific ether ester compound and a specific ester condensate. The spunbond nonwoven fabric made of polyolefin-based synthetic fibers of the present invention is characterized in that a treatment agent for non-woven fabrics made of polyolefin-based synthetic fibers is adhered.

Description

Treatment agent for non-woven fabrics made of polyolefin-based synthetic fibers, polyolefin-based synthetic fibers, and spunbond non-woven fabrics made of polyolefin-based synthetic fibers

The present invention relates to a treatment agent for non-woven fabrics made of polyolefin-based synthetic fibers, polyolefin-based synthetic fibers, and spunbond non-woven fabrics made of polyolefin-based synthetic fibers.

In general, a polyolefin-based synthetic fiber is used as the raw material fiber of the nonwoven fabric. For example, nonwoven fabrics are produced by a spunbonding method using polyolefin-based synthetic fibers. The non-woven fabric produced by the spunbond method is called spunbond non-woven fabric. By coating the non-woven fabric with an oil agent as a non-woven fabric treatment agent, the non-woven fabric can be imparted with functions such as durable hydrophilicity. Non-woven fabrics endowed with functions such as durable hydrophilicity are used in a wide range of fields such as hygiene, medical, and civil engineering.

Patent Document 1 discloses a water permeability imparting agent containing an alkylene oxide adduct of a polyvalent active hydrogen compound as a treatment agent for nonwoven fabrics. As a polyvalent active hydrogen compound, Patent Document 1 discloses a partial ester of a polyhydric alcohol having a valence of 3 to 6 and a fatty acid.

prior art literature Patent Literature Patent Document 1: International Publication No. 2016/121673

The problem to be solved by the invention However, in order to more effectively impart a function to the nonwoven fabric, it is necessary to apply the nonwoven fabric treatment agent more uniformly to the fibers constituting the nonwoven fabric. On the other hand, in order to apply the treatment agent for nonwoven fabrics more uniformly, it is necessary to improve the wettability of the treatment agent for nonwoven fabrics with respect to the fibers constituting the nonwoven fabric. However, once the wettability of the nonwoven fabric treatment agent is improved, the durable hydrophilicity of the nonwoven fabric tends to decrease easily. Therefore, it is a current subject to preferably improve both the wettability of the nonwoven fabric treatment agent and the durable hydrophilicity of the nonwoven fabric.

In view of the above-mentioned facts, the present invention aims to provide a treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers, which can preferably improve the wettability of fibers constituting nonwoven fabrics, and also improve the durable hydrophilicity of the nonwoven fabrics. Further, the present invention provides a polyolefin-based synthetic fiber to which the treatment agent for polyolefin-based synthetic fiber nonwoven fabrics is adhered, and a polyolefin-based synthetic fiber-made spunbond nonwoven fabric to which the treatment agent for polyolefin-based synthetic fiber nonwoven fabrics is adhered. .

means of solving problems The processing agent for nonwoven fabrics made of polyolefin-based synthetic fibers for solving the above-mentioned problems is characterized by containing at least one of the following first ether ester compound and the following second ether ester compound, and the following ester condensate. 1st ether ester compound: The compound which added the alkylene oxide of carbon number 2-4 to 1 mol of the ester compound which a polyhydric alcohol and a monobasic fatty acid formed in a total ratio of 1-500 mol. Second ether ester compound: a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to 1 mol of an ester compound formed by a polyhydric alcohol and a monobasic fatty acid in a total ratio of 1 to 500 mol, and a compound having 4 to 26 carbon atoms. A compound formed by the condensation of fatty acids. Ester condensate: a condensate having a structural unit formed of a hydroxycarboxylic acid having 6 to 22 carbon atoms and a degree of condensation of 1 to 5, wherein the hydroxycarboxylic acid has a hydroxyl group and a carboxyl group in the molecule.

It is preferable that the content rate of the said ester condensate is 0.01-20 mass % of the said processing agent for nonwoven fabrics made from a polyolefin type synthetic fiber.

The treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers preferably contains a selected amount when the total content of the first ether ester compound, the second ether ester compound, and the ester condensate is 100 parts by mass. A ratio of 80 to 99.95 parts by mass of at least one of the first ether ester compound and the second ether ester compound and 0.05 to 20 parts by mass of the ester condensate.

（化1中 R ¹：碳數4～12的飽和烴基、或碳數4～12的不飽和烴基， R ²：氫原子、或碳數1～8的飽和烴基。） As for the treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers, it is preferable that the hydroxycarboxylic acid is represented by the following formula 1.

(In Chemical 1, R ¹ : a saturated hydrocarbon group having 4 to 12 carbon atoms, or an unsaturated hydrocarbon group having 4 to 12 carbon atoms, and R ² : a hydrogen atom, or a saturated hydrocarbon group having 1 to 8 carbon atoms.)

In the above-mentioned treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers, it is preferable that R ¹ in the above-mentioned compound 1 is a saturated hydrocarbon group having 8 to 10 carbon atoms, or an unsaturated hydrocarbon group having 8 to 10 carbon atoms.

In the above-mentioned treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers, it is preferable that R ² in the above-mentioned compound 1 is a saturated hydrocarbon group having 6 to 8 carbon atoms.

It is preferable that the said ester condensate has a degree of condensation 1-2, and it has a cyclic molecular structure as the processing agent for the said polyolefin type synthetic fiber nonwoven fabric.

The polyolefin-based synthetic fibers for solving the above-mentioned problems are characterized in that the above-mentioned treatment agent for nonwoven fabrics made of the polyolefin-based synthetic fibers is adhered.

The point of the spunbond nonwoven fabric made of polyolefin-based synthetic fibers for solving the above-mentioned problems is that the above-mentioned treatment agent for non-woven fabrics made of polyolefin-based synthetic fibers is adhered.

Invention effect According to the present invention, the wettability of the treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers can be preferably improved with respect to the fibers constituting the non-woven fabrics made of polyolefin-based synthetic fibers, and the durable hydrophilicity of the nonwoven fabrics made of polyolefin-based synthetic fibers can be preferably improved .

(first embodiment) The first embodiment of the present invention, that is, a treatment agent for a nonwoven fabric made of polyolefin-based synthetic fibers (hereinafter simply referred to as a treatment agent) will be described.

The processing agent of this embodiment contains at least one of the following 1st ether ester compound and the following 2nd ether ester compound, and the following ester condensate.

1st ether ester compound: The compound which added the alkylene oxide of carbon number 2-4 to 1 mol of the ester compound which a polyhydric alcohol and a monobasic fatty acid formed in a total ratio of 1-500 mol.

Second ether ester compound: a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to 1 mol of an ester compound formed by a polyhydric alcohol and a monobasic fatty acid in a total ratio of 1 to 500 mol, and a compound having 4 to 26 carbon atoms. A compound formed by the condensation of fatty acids.

Ester condensate: a condensate having a structural unit formed of a hydroxycarboxylic acid having 6 to 22 carbon atoms and a degree of condensation of 1 to 5, wherein the hydroxycarboxylic acid has a hydroxyl group and a carboxyl group in the molecule.

When the treating agent contains at least one of the first ether ester compound and the second ether ester compound, and the ester condensate, the wettability of the treating agent to fibers constituting a nonwoven fabric made of polyolefin-based synthetic fibers, as described later will be better improved. In addition, the durable hydrophilicity of the nonwoven fabric made of polyolefin-based synthetic fibers to which the treatment agent has adhered can be preferably improved.

The above-mentioned polyol is not particularly limited, and may be an aliphatic polyol or an aromatic polyol. In addition, the aliphatic polyol may be saturated aliphatic or unsaturated aliphatic.

Specific examples of the above-mentioned polyhydric alcohol include, for example, ethylene glycol, glycerin, sorbitan, trimethylolpropane, and the like.

The above-mentioned polyols may be used alone or in combination of two or more.

The above-mentioned monobasic fatty acid is not particularly limited, and may be a straight-chain fatty acid or a branched fatty acid. Moreover, a saturated fatty acid may be sufficient and an unsaturated fatty acid may be sufficient.

Specific examples of the monobasic fatty acid include, for example, 12-hydroxystearic acid, ricinoleic acid, lauric acid, stearic acid, oleic acid, valeric acid, caprylic acid, and the like.

The said monobasic fatty acid may be used individually by 1 type, and may be used in combination of 2 or more types.

In addition, the ester compound formed by the above-mentioned polyhydric alcohol and monobasic fatty acid may be a natural oil. Specific examples of natural oils and fats include, for example, coconut oil, rapeseed oil, sunflower oil, soybean oil, castor oil, hardened castor oil, sesame oil, fish oil, and tallow.

The said natural fats and oils may be used individually by 1 type, and may be used in combination of 2 or more types.

Specific examples of the above-mentioned alkylene oxide having 2 to 4 carbon atoms include, for example, ethylene oxide, propylene oxide, butylene oxide, and the like. Among these, ethylene oxide is preferred. The polymerization arrangement is not particularly limited, and may be a random adduct or a block adduct.

The above-mentioned alkylene oxides having 2 to 4 carbon atoms may be used alone or in combination of two or more.

The added mole number of the alkylene oxide having 2 to 4 carbon atoms is preferably 5 to 120 moles.

Among the first ether ester compound and the second ether ester compound, the ester compound may be the same or different. The same applies to the alkylene oxide having 2 to 4 carbon atoms, and the first ether ester compound and the second ether ester compound may be the same or different.

The fatty acid having 4 to 26 carbon atoms in the second ether ester compound is not particularly limited, and may be a straight-chain fatty acid or a branched fatty acid. Moreover, a saturated fatty acid may be sufficient and an unsaturated fatty acid may be sufficient.

Specific examples of the fatty acid having 4 to 26 carbon atoms include lauric acid, oleic acid, stearic acid, caprylic acid, succinic acid, maleic acid, and the like.

The fatty acids having 4 to 26 carbon atoms may be used alone or in combination of two or more.

（化2中 R ¹：碳數4～12的飽和烴基、或碳數4～12的不飽和烴基， R ²：氫原子、或碳數1～8的飽和烴基。） The hydroxycarboxylic acid having 6 to 22 carbon atoms in the constituent unit of the ester condensate is preferably represented by the following formula 2. 2

(In Chemical 2, R ¹ : a saturated hydrocarbon group having 4 to 12 carbon atoms, or an unsaturated hydrocarbon group having 4 to 12 carbon atoms, and R ² : a hydrogen atom, or a saturated hydrocarbon group having 1 to 8 carbon atoms.)

In Compound 2, R ¹ is preferably a saturated hydrocarbon group having 8 to 10 carbon atoms or an unsaturated hydrocarbon group having 8 to 10 carbon atoms.

R ² in Compound 2 is preferably a saturated hydrocarbon group having 6 to 8 carbon atoms. When the carbon number of the saturated hydrocarbon group is 6 to 8, the durable hydrophilicity of the nonwoven fabric made of polyolefin-based synthetic fibers can be further preferably improved.

The above-mentioned ester condensate preferably has a degree of condensation of 1 to 2 and has a cyclic molecular structure.

The content ratio of the ester condensate in the treatment agent is not particularly limited. The content ratio of the ester condensate in the treatment agent is preferably 0.01 to 20% by mass.

The content ratio of the first ether ester compound, the second ether ester compound, and the ester condensate in the treatment agent is not particularly limited. When the total content ratio of the first ether ester compound, the second ether ester compound, and the ester condensate is 100 parts by mass, the treatment agent preferably contains at least one selected from the group consisting of the first ether ester compound and the second ether ester compound. 80-99.95 mass parts of one, and the ratio of 0.05-20 mass parts of ester condensates.

By setting the content ratio of the first ether ester compound, the second ether ester compound, and the ester condensate within the above numerical range, the wettability of the treating agent to the fibers constituting the nonwoven fabric made of polyolefin-based synthetic fibers will be affected as described later. further improved. In addition, the durable hydrophilicity of the nonwoven fabric made of polyolefin-based synthetic fibers to which the treatment agent has adhered can be further preferably improved.

The treatment agent may also contain other ingredients.

Specific examples of other components include ionic surfactants such as anionic surfactants, cationic surfactants, and amphoteric surfactants that are amphoteric compounds, or nonionic surfactants, monohydric or polyhydric alcohols, fatty acids, and fatty acid esters. , wax compounds, polysiloxane compounds, etc.

As an ionic surfactant, a phosphate type ionic surfactant and a sulfonate type ionic surfactant are mentioned, for example. Specific examples of the phosphate type ionic surfactant include, for example, lauryl phosphate potassium salt, butyl phosphate potassium salt, and the like. Specific examples of the sulfonate type ionic surfactant include alkyl (12 to 16 carbon atoms) sulfonic acid sodium salts, for example.

As a nonionic surfactant, a polyether type nonionic surfactant, an ether type nonionic surfactant, an ester type nonionic surfactant, etc. are mentioned, for example. Specific examples of ether-type nonionic surfactants include compounds obtained by adding 10 mols of ethylene oxide to 1 mol of lauryl alcohol, and 120 mols of propylene oxide added to 1 mol of neotaerythritol. formed compounds.

Specific examples of the ester-type nonionic surfactant include, for example, a compound obtained by adding 1 mol of stearic acid to 20 mol of ethylene oxide.

These other components may be used individually by 1 type, and may be used in combination of 2 or more types.

The content ratio of other components in the treatment agent is not particularly limited. It is preferable that a processing agent contains the ratio of 1-30 mass parts of other components with respect to 100 mass parts of total content ratios of a 1st ether ester compound, a 2nd ether ester compound, and an ester condensate.

(Second Embodiment) The second embodiment of the present invention, that is, a polyolefin-based synthetic fiber and a spunbond nonwoven fabric made of a polyolefin-based synthetic fiber will be described. The treatment agent of the first embodiment adheres to the polyolefin-based synthetic fiber of the present embodiment.

Here, the so-called polyolefin synthetic fiber means a synthetic fiber synthesized by using olefin (olefine, alkene) as a monomer. Hereinafter, the polyolefin synthetic fibers are simply referred to as synthetic fibers.

Specific examples of synthetic fibers include polyethylene-based fibers, polypropylene-based fibers, and polybutene-based fibers. These may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, polypropylene fibers can also be applied to modified polypropylene fibers obtained by copolymerizing various monomers, and composite polypropylene fibers formed of polyethylene and polypropylene.

In addition, it can also be a composite fiber with a core-sheath structure, that is, a composite fiber in which either or both of the core and the sheath are polyolefin fibers, such as polyethylene/polypropylene composite fibers with polyethylene fibers in the sheath, Vinyl/polyester composite fiber.

The amount of adhering the treating agent of the first embodiment to the synthetic fibers is not particularly limited, but the treating agent (excluding the solvent) is preferably adhering to 0.1 to 2 mass % with respect to the synthetic fibers, more preferably 0.3 to 1.2 mass %. .

As a method of adhering the treatment agent to the synthetic fibers, for example, the following method can be applied: using an aqueous solution containing the treatment agent of the first embodiment and water, or a further diluted aqueous solution, by a known method such as a dipping method, a spray method, The roller method, the pilot oil method using a metering pump, etc. make it adhere.

The polyolefin-based synthetic fiber spunbond nonwoven fabric (hereinafter simply referred to as a nonwoven fabric) of the present invention is produced by a spunbond method.

The manufacturing method of the nonwoven fabric of the spunbond method is preferably carried out through the following steps 1-7.

Step 1: a raw material supply step, supplying raw resin of synthetic fibers to an extruder.

Step 2: In the melting and extrusion step, the raw resin is heated and melted in the extruder, and then pushed to the nozzle with the spinning bobbin.

Step 3: In the spinning and stretching step, melt spinning is performed from a nozzle, and the melt-spun fibers are stretched using an ejector.

Step 4: Capture and transport step, capture the fibers passing through the above step 3 to the conveyor belt to form a carded web, and then transport the carded web by the conveyor belt.

Step 5: the fusion step, the carded web passing through the above step 4 is passed between a pair of heated drums to fuse the fibers.

Step 6: An adhesion step in which the treatment agent of the first embodiment is attached to the nonwoven fabric formed by the above-mentioned Step 5.

Step 7: winding step, winding the non-woven fabric that has passed the above step 6 onto the winding drum.

By going through the above steps, the nonwoven fabric of the present embodiment can be produced.

According to the treating agent of the first embodiment, and the synthetic fibers and nonwoven fabrics of the second embodiment, the following effects can be obtained.

(1) The treating agent of the first embodiment contains a specific ether ester compound and a specific ester condensate. Therefore, the wettability of the treating agent with respect to the polyolefin-based synthetic fiber is preferably improved.

(2) By adhering the treatment agent of the first embodiment, the durable hydrophilicity of the spunbond nonwoven fabric made of polyolefin-based synthetic fibers can be preferably improved.

The above-described embodiment may be modified and implemented as follows. The above-described embodiment and the following modifications can be implemented in combination with each other within a technically non-contradictory range.

・In the second embodiment, the synthetic fiber to which the treatment agent is adhered is a polyolefin-based synthetic fiber, but it is not limited to this aspect. The treatment agent may be attached to synthetic fibers other than polyolefin-based synthetic fibers. Similarly, a treatment agent may be attached to a spunbond nonwoven fabric made of synthetic fibers other than polyolefin-based synthetic fibers. Synthetic fibers other than polyolefin-based synthetic fibers include, for example, polyester-based fibers, polyamide-based fibers, polyacrylonitrile-based fibers, cellulose-based fibers, lignin-based fibers, and the like. These fibers may be composite synthetic fibers composed of two or more types.

Specific examples of polyester-based fibers include polyethylene terephthalate (PET), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polylactic acid. , Composite polyester fibers, etc., containing these polyester resins. In addition, as the polyester-based fibers, modified polyester fibers such as alkaline or acid dyeable polyester fibers, antistatic polyester fibers, and flame-retardant polyester fibers, etc., can be mentioned.

・In addition, although the nonwoven fabric to which the treatment agent adheres is a spunbond nonwoven fabric, it is not limited to this aspect. The treating agent can also be attached to non-woven fabrics other than spunbond non-woven fabrics. The so-called non-woven fabrics other than spunbond non-woven fabrics refer to non-woven fabrics formed by a method other than spunbond to form a carded web.

As a method of forming a card web other than the spunbond method, when the raw material fibers are short fibers, for example, dry methods such as a card-laying method and an air-laid method, and a wet method such as a papermaking method are exemplified. Moreover, when the raw material fiber is a long fiber, a melt blowing method or a flash spinning method can be mentioned. In addition, the bonding method between fibers includes a chemical bonding method, a thermally conductive bonding method, a pinhole method, a water needle method, a stitch bonding method, and the like.

・As long as the effects of the present invention are not impaired, the treatment agent may contain stabilizers, antistatic agents, charge inhibitors, adhesives, antioxidants, ultraviolet absorbers, and antifoaming agents for maintaining the quality of the treatment agents (polysiloxane-based compound) and other components that are commonly used as treatment agents.

Example

Hereinafter, in order to demonstrate the structure and effect of this invention more concretely, although an Example etc. are given, this invention is not limited to these Examples. In addition, in the following description of an Example and a comparative example, % represents mass %.

Test Category 1 (Preparation of Treatment Agent for Polyolefin-Based Synthetic Fiber Nonwoven Fabric)

(Examples 1 to 40 and Comparative Examples 1 to 7) The first ether ester compounds (A1-1 to A1-10) shown in Tables 1 and 2 were prepared by the following method. Among them, in A1-1 to A1-4 shown in Table 1, natural oils and fats were used as the ester compound of a polyhydric alcohol and a monobasic fatty acid.

In A1-1, 933 g (1 mol) of castor oil and 2 g of sodium hydroxide as a catalyst were added to the autoclave, and the gas atmosphere was replaced with nitrogen, and then 4400 g (100 mol) of ethylene oxide was press-blended. , the etherification reaction is carried out.

Next, 40 g of a known inorganic synthetic adsorbent was added to the liquid subjected to the etherification reaction, and the mixture was stirred at about 80° C. for 30 minutes. Then, it was moved to the filter precoated with diatomaceous earth, and the inorganic synthetic adsorbent which adsorb|sucked the sodium hydroxide catalyst was removed, and A1-1 was prepared. A1-2 to A1-4 are also prepared according to the synthesis method of A1-1.

In the first ether ester compound, the type and molar number of the ester compound, and the type and molar number of the alkylene oxide are shown in the "ester compound" column and the "alkylene oxide" column in Table 1, respectively.

Table 1 Types of the first ether ester compound ester compound Alkylene oxide type Molar number type Molar number A1-1 castor oil 1 ethylene oxide 100 A1-2 castor oil 1 ethylene oxide propylene oxide 15 6 A1-3 hardened castor oil 1 ethylene oxide 20 A1-4 hardened castor oil 1 ethylene oxide propylene oxide 40 12

As shown in Table 2, in A1-5, 62 g (1 mol) of ethylene glycol as a polyhydric alcohol and 600 g (2 mol) of 12-hydroxystearic acid as a monobasic fatty acid were charged into a reaction vessel, and the reaction vessel was subjected to esterification. chemical reaction. The ester compound obtained by the esterification reaction and 2 g of potassium hydroxide as a catalyst were added to the autoclave, and the gas atmosphere was replaced with nitrogen, and then 1408 g (32 mol) of ethylene oxide was press-blended to carry out etherification. reaction.

Next, 17 g of a known inorganic synthetic adsorbent was added to the liquid subjected to the etherification reaction, and the mixture was stirred at about 80° C. for 30 minutes. Then, this was moved to a filter pre-coated with diatomaceous earth, and the inorganic synthetic adsorbent to which the potassium hydroxide catalyst was adsorbed was removed to prepare A1-5. A1-6 to A1-10 are also prepared according to the synthesis method of A1-5.

In the first ether ester compound, the type and molar number of the ester compound, and the type and molar number of the alkylene oxide are shown in the "ester compound" column and the "alkylene oxide" column in Table 2, respectively.

Table 2 Types of the first ether ester compound ester compound Alkylene oxide Polyol Molar number Monobasic fatty acids Molar number type Molar number A1-5 Ethylene Glycol 1 12-Hydroxystearic acid 2 ethylene oxide 32 A1-6 glycerin 1 Ricinoleic acid 3 ethylene oxide 25 A1-7 Sorbitol 1 12-Hydroxystearic acid 4 ethylene oxide 20 A1-8 glycerin 1 Lauric acid 1 ethylene oxide 75 A1-9 glycerin 1 Stearic acid 1 ethylene oxide 26 A1-10 glycerin 1 Oleic acid 1 ethylene oxide twenty two

Further, the second ether ester compounds (A2-1 to A2-20, Ra-1, Ra-2) shown in Tables 3 and 4 were prepared by the following methods. Among them, in A2-1 to A2-12 shown in Table 3, natural oils and fats were used as the ester compound formed by a polyhydric alcohol and a monobasic fatty acid.

In A2-1, 933 g (1 mol) of castor oil and 2 g of sodium hydroxide as a catalyst were added to the autoclave, and the atmosphere was replaced with nitrogen, and then 660 g (15 mol) of ethylene oxide was press-blended. With 348 g (6 moles) of propylene oxide, etherification reaction was carried out.

Next, 16 g of a known inorganic synthetic adsorbent was added to the liquid subjected to the etherification reaction, and the mixture was stirred at about 80° C. for 30 minutes. Then, it was moved to the filter pre-coated with diatomaceous earth, and the inorganic synthetic adsorbent which adsorb|sucked the sodium hydroxide catalyst was removed.

The liquid from which the sodium hydroxide catalyst was removed and 600 g (3 mol) of lauric acid, which is a fatty acid having 4 to 26 carbon atoms, were charged into a reaction vessel, and esterification reaction was performed to prepare A2-1. A2-2 to A2-12 are also modulated according to the synthesis method of A2-1.

In the second ether ester compound, the types and molar numbers of ester compounds, the types and molar numbers of alkylene oxides, and the types and molar numbers of fatty acids having 4 to 26 carbon atoms are shown in the column "Ester compound" in Table 3, respectively. "Alkylene oxide" column, "Fatty acid" column.

table 3 Types of the second ether ester compound ester compound Alkylene oxide fatty acid type Molar number type Molar number type Molar number A2-1 castor oil 1 ethylene oxide propylene oxide 15 6 Lauric acid 3 A2-2 hardened castor oil 1 ethylene oxide 20 Lauric acid 3 A2-3 hardened castor oil 1 ethylene oxide 30 Oleic acid 3 A2-4 hardened castor oil 1 ethylene oxide propylene oxide 30 12 Stearic acid 3 A2-5 hardened castor oil 1 ethylene oxide 83 Lauric acid 3 A2-6 hardened castor oil 1 ethylene oxide propylene oxide 30 7 bitter 3 A2-7 hardened castor oil 1 ethylene oxide 28 Stearic acid 2 A2-8 hardened castor oil 1 ethylene oxide twenty three succinic acid 2 A2-9 hardened castor oil 1 ethylene oxide propylene oxide 15 10 Oleic acid 1 A2-10 hardened castor oil 1 ethylene oxide 7 Oleic acid 3 A2-11 hardened castor oil 1 ethylene oxide 30 Maleic Stearic Acid 1 1 A2-12 hardened castor oil 1 ethylene oxide 10 maleic acid 1

As shown in Table 4, in A2-13, 62 g (1 mol) of ethylene glycol as a polyhydric alcohol and 600 g (2 mol) of 12-hydroxystearic acid as a monobasic fatty acid were charged into a reaction vessel, and the reaction vessel was subjected to esterification. chemical reaction. The ester compound obtained by the esterification reaction and 2 g of potassium hydroxide as a catalyst were added to the autoclave, and the gas atmosphere was replaced with nitrogen, and then 1408 g (32 mol) of ethylene oxide was press-blended to carry out etherification. reaction.

Next, 17 g of a known inorganic synthetic adsorbent was added to the liquid subjected to the etherification reaction, and the mixture was stirred at 80° C. for 30 minutes. Then, it was moved to the filter pre-coated with diatomaceous earth, and the inorganic synthetic adsorbent which adsorb|sucked the potassium hydroxide catalyst was removed.

The liquid from which the potassium hydroxide catalyst was removed and 847 g (3 moles) of oleic acid, which is a fatty acid having 4 to 26 carbon atoms, were charged into a reaction vessel, and esterification reaction was performed to prepare A2-13. A2-14 to A2-20, Ra-1, and Ra-2 were also modulated according to the synthesis method of A2-13.

In the second ether ester compound, the types and molar numbers of ester compounds, the types and molar numbers of alkylene oxides, and the types and molar numbers of fatty acids having 4 to 26 carbon atoms are shown in the column "Ester compound" in Table 4, respectively. "Alkylene oxide" column, "Fatty acid" column.

Table 4 Types of the second ether ester compound ester compound Alkylene oxide fatty acid Polyol Molar number Monobasic fatty acids Molar number type Molar number type Molar number A2-13 Ethylene Glycol 1 12-Hydroxystearic acid 2 ethylene oxide 32 Oleic acid 3 A2-14 glycerin 1 Ricinoleic acid 3 ethylene oxide 13 Lauric acid 3 A2-15 Trimethylolpropane 1 12-Hydroxystearic acid 3 ethylene oxide 25 Oleic acid 3 A2-16 glycerin 1 Stearic acid 1 ethylene oxide 26 Lauric acid 2 A2-17 glycerin 1 12-Hydroxystearic acid 1 ethylene oxide twenty two Lauric acid 2 A2-18 Sorbitol 1 Valeric acid 2 ethylene oxide 28 Oleic acid 2 A2-19 Sorbitol 1 12-Hydroxystearic acid 4 ethylene oxide twenty two Oleic acid 4 A2-20 glycerin 1 bitter 1 ethylene oxide 40 Lauric acid 3 Ra-1 lauryl alcohol 1 12-Hydroxystearic acid 1 ethylene oxide 30 Lauric acid 1 Ra-2 glycerin 1 12-Hydroxystearic acid 3 - - Oleic acid 2

Furthermore, ester condensates (B-1 to B-21, Rb-1 to Rb-3) shown in Table 5 were prepared. These ester condensates may be commercially available, and may be produced by a known method. When it manufactures by a well-known method, for example, it can manufacture by the dehydration condensation reaction between the hydroxyl group contained in a raw material material, and a carboxyl group.

In Table 5, R ¹ and R ² mean a hydrocarbon group or a hydrogen atom in the hydroxycarboxylic acid having 6 to 22 carbon atoms shown in Formula 2 above.

The type of R ¹ , the type of R ² , the carbon number, degree of condensation, and molecular structure of the hydroxycarboxylic acid in the ester condensate are shown in the columns of "R ¹ ", "R ² ", "carbon number", "Condensation degree" column, "Molecular structure" column. Here, in the column of "molecular structure", "0" in the column of "cyclic" means having a cyclic molecular structure, and "0" in the column of "chain" means having a molecular structure in a chain shape.

table 5 Types of Ester Condensates R ¹ R ² carbon number Degree of condensation molecular structure ring chain B-1 Unsaturated hydrocarbon group with 10 carbon atoms and 1 double bond Saturated hydrocarbon group with 6 carbon atoms 18 1 〇 B-2 Saturated hydrocarbon group with 10 carbon atoms Saturated hydrocarbon group with 6 carbon atoms 18 1 〇 B-3 Unsaturated hydrocarbon group with 9 carbon atoms and 1 double bond Saturated hydrocarbon group of carbon number 7 18 1 〇 B-4 Saturated hydrocarbon group with 8 carbon atoms Saturated hydrocarbon group with 8 carbon atoms 18 1 〇 B-5 Unsaturated hydrocarbon group with 10 carbon atoms and 1 double bond Saturated hydrocarbon group with 6 carbon atoms 18 2 〇 B-6 Saturated hydrocarbon group with 10 carbon atoms Saturated hydrocarbon group with 6 carbon atoms 18 2 〇 B-7 Unsaturated hydrocarbon group with 8 carbons and 2 double bonds Saturated hydrocarbon group with 8 carbon atoms 18 2 〇 B-8 Saturated hydrocarbon group of carbon number 12 Saturated hydrocarbon group of carbon number 4 18 1 〇 B-9 Saturated hydrocarbon group of carbon number 12 A hydrogen atom 14 1 〇 B-10 Saturated hydrocarbon group with 6 carbon atoms Saturated hydrocarbon group with 8 carbon atoms 16 1 〇 B-11 Saturated hydrocarbon group of carbon number 4 A hydrogen atom 6 2 〇 B-12 Saturated hydrocarbon group with 10 carbon atoms Saturated hydrocarbon group of carbon number 4 16 2 〇 B-13 Unsaturated hydrocarbon group with 10 carbon atoms and 1 double bond Saturated hydrocarbon group with 6 carbon atoms 18 3 〇 B-14 Saturated hydrocarbon group with 6 carbon atoms Saturated hydrocarbon group with 6 carbon atoms 14 3 〇 B-15 Unsaturated hydrocarbon group with 12 carbon atoms and 1 double bond A hydrogen atom 14 2 〇 B-16 Unsaturated hydrocarbon group with 10 carbon atoms and 1 double bond Saturated hydrocarbon group with 6 carbon atoms 18 2 〇 B-17 Saturated hydrocarbon group with 10 carbon atoms Saturated hydrocarbon group with 6 carbon atoms 18 2 〇 B-18 Saturated hydrocarbon group of carbon number 7 Saturated hydrocarbon group with 3 carbon atoms 12 3 〇 B-19 Saturated hydrocarbon group of carbon number 14 A hydrogen atom 16 1 〇 B-20 Saturated hydrocarbon group with 3 carbon atoms Saturated hydrocarbon group of carbon number 1 6 4 〇 B-21 Unsaturated hydrocarbon group with 16 carbon atoms and 1 double bond A hydrogen atom 18 2 〇 Rb-1 Saturated hydrocarbon group with 2 carbon atoms A hydrogen atom 4 2 〇 Rb-2 Saturated hydrocarbon group of carbon number 12 Saturated hydrocarbon group with 10 carbon atoms twenty four 1 〇 Rb-3 Saturated hydrocarbon group of carbon number 4 A hydrogen atom 6 6 〇

Next, using each component shown in Table 6, 99.5 parts by mass of the first ether ester compound (A1-1) and 0.5 parts by mass of the ester condensate (B-1) were added to the beaker. These were sufficiently stirred to prepare the treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers of Example 1.

The treatment agents for nonwoven fabrics made of polyolefin-based synthetic fibers of Examples 2 to 40 and Comparative Examples 1 to 7 were prepared in the same manner as in Example 1 using the components shown in Table 6. The types and contents of ether ester compounds, the types and contents of ester condensates, and the types and contents of other components in the treating agents of each example are shown in the column "Treatment agents for nonwoven fabrics made of polyolefin-based synthetic fibers" in Table 6, respectively. Ether ester compound (A)" column, "ester condensate (B)" column, "other component (C)" column.

Table 6 Treatment agent for non-woven fabrics made of polyolefin-based synthetic fibers Evaluation Ether ester compound (A) Ester condensate (B) Other ingredients (C) Process evaluation project Nonwoven Evaluation Project 1st ether ester compound 2nd ether ester compound type parts by mass type parts by mass type parts by mass type Parts by mass relative to the total of (A) and (B) 100 parts by mass wetness Durable hydrophilic Example 1 A1-1 99.5 - - B-1 0.5 - - ◎ ◎ Example 2 A1-2 99.9 - - B-2 0.1 - - ◎ ◎ Example 3 A1-3 99 - - B-3 1 - - ◎ ◎ Example 4 A1-4 90 - - B-4 10 - - ◎ ◎ Example 5 A1-5 85 - - B-2 15 - - ◎ ◎ Example 6 A1-6 99.95 - - B-5 0.05 - - ◎ ◎ Example 7 A1-7 99.9 - - B-6 0.1 - - ◎ ◎ Example 8 A1-8 99.5 - - B-7 0.5 - - ◎ ◎ Example 9 A1-9 99.8 - - B-1 0.2 C-1 10 ◎ ◎ Example 10 A1-10 99 - - B-2 1 - - ◎ ◎ Example 11 - - A2-1 98 B-3 2 C-2 15 ◎ ◎ Example 12 - - A2-2 99.5 B-4 0.5 - - ◎ ◎ Example 13 - - A2-3 98.5 B-1 B-2 1 0.5 - - ◎ ◎ Example 14 - - A2-13 A2-6 50 45 B-6 5 C-3 10 ◎ ◎ Example 15 - - A2-14 99.5 B-7 0.5 - - ◎ ◎ Example 16 - - A2-15 99 B-1 1 C-4 10 ◎ ◎ Example 17 - - A2-16 99 B-2 1 - - ◎ ◎ Example 18 - - A2-17 99 B-3 1 - - ◎ ◎ Example 19 - - A2-10 95 B-3 5 - - ◎ ◎ Example 20 - - A2-7 99 B-5 1 - - ◎ ◎ Example 21 - - A2-8 98 B-6 2 - - ◎ ◎ Example 22 - - A2-9 98 B-7 2 - - ◎ ◎ Example 23 - - A2-5 A2-10 50 48 B-4 2 - - ◎ ◎ Example 24 - - A2-11 99 B-6 B-7 0.5 0.5 - - ◎ ◎ Example 25 - - A2-12 99.99 B-1 0.01 - - 〇 〇 Example 26 - - A2-18 99.5 B-8 0.5 - - 〇 ◎ Example 27 - - A2-5 95 B-9 5 - - 〇 ◎ Example 28 - - A2-20 99.8 B-10 0.2 - - 〇 ◎ Example 29 A1-4 99.5 - - B-11 0.5 - - 〇 ◎ Example 30 A1-7 99 - - B-12 1 - - 〇 〇 Example 31 A1-9 99 - - B-13 1 - - 〇 ◎ Example 32 - - A2-3 99 B-16 1 - - 〇 ◎ Example 33 A1-8 90 - - B-17 10 - - 〇 ◎ Example 34 - - A2-14 95 B-13 5 - - 〇 ◎ Example 35 A1-10 99 - - B-14 1 C-5 20 〇 〇 Example 36 - - A2-1 99 B-15 1 - - 〇 〇 Example 37 - - A2-19 95 B-18 5 - - 〇 〇 Example 38 - - A2-16 97 B-19 3 - - 〇 〇 Example 39 - - A2-4 97 B-20 3 - - 〇 〇 Example 40 - - A2-13 97 B-21 3 C-7 20 〇 〇 Comparative Example 1 - - A2-19 100 - - - - × 〇 Comparative Example 2 - - Ra-1 99 B-2 1 - - 〇 × Comparative Example 3 - - Ra-2 99 B-3 1 - - 〇 × Comparative Example 4 - - A2-15 90 Rb-1 10 - - × 〇 Comparative Example 5 - - A2-16 90 Rb-2 10 - - × × Comparative Example 6 - - A2-18 95 Rb-3 5 - - × × Comparative Example 7 - - - - - - C-6 100 × 〇

Details of C-1 to C-7 described in the other component (C) column of Table 6 are as follows. C-1: Potassium Lauryl Phosphate C-2: Butyl Phosphate Potassium Salt C-3: Alkyl (carbon number 12-16) sulfonic acid sodium salt C-4: polyethylene glycol (molecular weight 600) C-5: Compound obtained by adding 1 mol of lauryl alcohol to 10 mol of ethylene oxide C-6: A compound obtained by adding 1 mol of neotaerythritol to 120 mol of propylene oxide C-7: Compound obtained by adding 1 mol of stearic acid to 20 mol of ethylene oxide

Test Category 2 (Manufacture of Polyolefin-Based Spunbond Nonwovens)

Using the treatment agent prepared in Test Category 1, a polyolefin-based spunbond nonwoven fabric was produced.

Specifically, the treatment agent prepared in Test Category 1 was diluted with water to obtain an aqueous liquid having a concentration of 0.25% by mass. Using this aqueous solution, a treatment tank (tank temperature of 25° C.) was prepared, and a polypropylene spunbond nonwoven fabric (weight 20 g/m 2 ) was immersed in the treatment tank for 5 minutes and then taken out. 2 g of this polypropylene spunbond nonwoven fabric was pressed with a rolling machine to adjust the pressing ratio so that the adhesion amount of the aqueous liquid was 4 g, and then air-dried at 80°C for 30 minutes to obtain a treated nonwoven fabric with a solid content adhesion amount of 0.5 mass %.

Test Category 3 (Evaluation)

Regarding the treatment agents of Examples 1 to 40 and Comparative Examples 1 to 7, the evaluation item of processability was evaluation of wettability to nonwoven fabrics. In addition, the evaluation item of the nonwoven fabric was to evaluate the durable hydrophilicity of the nonwoven fabric to which the treatment agent adhered. The sequence of each test is as follows.

(wetting) Each of the treatment agents described in Examples and Comparative Examples was heated to about 70°C. Each heated treatment agent was added to ion-exchanged water heated to about 50° C. with stirring to prepare a 10% aqueous solution of the treatment agent.

Next, the polypropylene nonwoven fabric to which the treating agent was not applied was humidified for 24 hours in a constant temperature room at 20° C. with a relative humidity of 60%.

10 μl of the 10% aqueous solution of each treatment agent was dropped onto the humidified non-woven fabric. The state in which the treatment agent permeated the nonwoven fabric was visually observed. The time until the treatment agent was completely permeated was measured and evaluated by the following evaluation criteria. The results are shown in the column "Wetting" in Table 6.

・Evaluation criteria for wettability ◎ (good): soaked in less than 4 seconds 〇 (acceptable): 4 seconds or more and less than 6 seconds to achieve penetration × (defective): It takes more than 6 seconds to penetrate

(durable hydrophilicity) The spunbond non-woven fabric produced in test category 2 was cut into small pieces of 10cm×10cm. The small piece of nonwoven fabric was humidified in a constant temperature room at 20°C with a relative humidity of 60% for 24 hours.

The humidified non-woven fabric was placed on a 5-layer filter paper. Next, a cylinder with an inner diameter of 1 cm opened at both ends was placed on the center portion of the nonwoven fabric so that the axial direction was the vertical direction.

10 ml of 0.9% physiological saline was injected into the cylinder. The state in which the physiological saline was absorbed by the nonwoven fabric was visually observed, and the time until the physiological saline was completely absorbed was measured.

Then, the non-woven fabric was taken out, and the non-woven fabric was blown with warm air at 40° C. for 90 minutes to be air-dried. After drying by blowing air, the test of moisturizing the non-woven fabric and absorbing physiological saline was repeated three times. The results of the third time were evaluated by the following evaluation criteria. The results are shown in the column "Durable hydrophilicity" in Table 6.

・Evaluation criteria for durable hydrophilicity ◎ (good): The time required for the physiological saline to be completely absorbed is less than 5 seconds 〇 (Fair): The time required for the physiological saline to be completely absorbed is more than 5 seconds and less than 7 seconds × (defective): The time required for the physiological saline to be completely absorbed is 7 seconds or more

As can be seen from the results in Table 6, according to the present invention, the wettability of the treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers with respect to polyolefin-based synthetic fibers can be preferably improved. In addition, the durable hydrophilicity of the polyolefin-based synthetic fiber spunbond nonwoven fabric to which the treatment agent for the polyolefin-based synthetic fiber nonwoven fabric is adhered can also be preferably improved.

The present invention also includes the following aspects.

(Appendix 1) A treatment agent for nonwoven fabrics, comprising at least one of the following first ether ester compound and the following second ether ester compound, and the following ester condensate, The first ether ester compound: a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to 1 mol of an ester compound formed by a polyhydric alcohol and a monobasic fatty acid in a total ratio of 1 to 500 mol, Second ether ester compound: a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to 1 mol of an ester compound formed by a polyhydric alcohol and a monobasic fatty acid in a total ratio of 1 to 500 mol, and a compound having 4 to 26 carbon atoms. A compound formed from the condensation of fatty acids, Ester condensate: a condensate having a structural unit formed of a hydroxycarboxylic acid having 6 to 22 carbon atoms and a degree of condensation of 1 to 5, wherein the hydroxycarboxylic acid has a hydroxyl group and a carboxyl group in the molecule.

(Appendix 2) The treatment agent for nonwoven fabrics according to Appendix 1, wherein the content of the ester condensate is 0.01 to 20% by mass

(Appendix 3) The treating agent for nonwoven fabrics according to appendix 1 or 2, wherein when the total of the content ratios of the first ether ester compound, the second ether ester compound, and the ester condensate is set to 100 parts by mass, it contains a compound selected from the group consisting of the above A ratio of at least one of the first ether ester compound and the second ether ester compound of 80 to 99.95 parts by mass and the ester condensate of 0.05 to 20 parts by mass.

（R ¹：碳數4～12的飽和烴基、或碳數4～12的不飽和烴基， R ²：氫原子、或碳數1～8的飽和烴基。） (Appendix 4) The treatment agent for nonwoven fabrics according to any one of Appendices 1 to 3, wherein the hydroxycarboxylic acid is represented by the following formula 3. 3

(R ¹ : a saturated hydrocarbon group having 4 to 12 carbon atoms, or an unsaturated hydrocarbon group having 4 to 12 carbon atoms, R ² : a hydrogen atom, or a saturated hydrocarbon group having 1 to 8 carbon atoms.)

(Appendix 5) The treatment agent for nonwoven fabrics according to Appendix 4, wherein R ¹ in the above-mentioned compound 3 is a saturated hydrocarbon group having 8 to 10 carbon atoms, or an unsaturated hydrocarbon group having 8 to 10 carbon atoms.

(Appendix 6) The treatment agent for nonwoven fabrics according to Appendix 4 or 5, wherein R ² in the above-mentioned compound 3 is a saturated hydrocarbon group having 6 to 8 carbon atoms.

(Appendix 7) The treatment agent for nonwoven fabrics according to any one of Appendices 1 to 6, wherein the ester condensate has a degree of condensation of 1 to 2 and has a cyclic molecular structure.

(Appendix 8) A polyolefin-based synthetic fiber characterized in that the treatment agent for nonwoven fabrics according to any one of Appendices 1 to 7 is attached.

(Appendix 9) A spunbond nonwoven fabric is characterized in that: the treatment agent for nonwoven fabrics according to any one of appendixes 1 to 7 is attached.

Claims (9)

A treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers, comprising at least one of the following first ether ester compound and the following second ether ester compound, and the following ester condensate, the first ether ester compound : A compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to 1 mol of an ester compound formed by a polyhydric alcohol and a monobasic fatty acid in a total ratio of 1 to 500 mol, and the second ether ester compound: to a polyhydric alcohol and The ester compound formed by monobasic fatty acid is a compound formed by adding a compound formed by adding an alkylene oxide having 2 to 4 carbon atoms and a fatty acid having 4 to 26 carbon atoms in a total ratio of 1 to 500 moles. Product: a condensate having a structural unit formed of a hydroxycarboxylic acid having a carbon number of 6 to 22 and a degree of condensation of 1 to 5, and the hydroxycarboxylic acid has a hydroxyl group and a carboxyl group in the molecule. The treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers according to claim 1, wherein the content of the ester condensate is 0.01 to 20% by mass. The treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers according to claim 1 or 2, wherein the total of the content ratios of the first ether ester compound, the second ether ester compound, and the ester condensate is 100 mass In the case of parts, at least one selected from the group consisting of the first ether ester compound and the second ether ester compound is contained in a ratio of 80 to 99.95 parts by mass and 0.05 to 20 parts by mass of the ester condensate. The treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers according to claim 1 or 2, wherein the hydroxycarboxylic acid is represented by the following formula 1,

(In Compound 1, R ¹ : a saturated hydrocarbon group having 4 to 12 carbon atoms, or an unsaturated hydrocarbon group having 4 to 12 carbon atoms, and R ² : a hydrogen atom, or a saturated hydrocarbon group having 1 to 8 carbon atoms). The treating agent for nonwoven fabrics made of polyolefin-based synthetic fibers according to claim 4, wherein R ¹ in the compound 1 is a saturated hydrocarbon group having 8 to 10 carbon atoms, or an unsaturated hydrocarbon group having 8 to 10 carbon atoms. The treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers according to claim 4, wherein R ² in the above formula 1 is a saturated hydrocarbon group having 6 to 8 carbon atoms. The treatment agent for nonwoven fabrics made of polyolefin-based synthetic fibers according to claim 1 or 2, wherein the ester condensate has a degree of condensation of 1 to 2 and has a cyclic molecular structure. A polyolefin-based synthetic fiber characterized by adhering the treatment agent for a nonwoven fabric made of a polyolefin-based synthetic fiber according to any one of claims 1 to 7. A spunbond nonwoven fabric made of polyolefin-based synthetic fibers, characterized in that: the treatment agent for non-woven fabrics made of polyolefin-based synthetic fibers according to any one of claims 1 to 7 is adhered.