JP7313629B2 - Surface treatment agent - Google Patents

Description

The present invention relates to a surface treatment agent. More particularly, it relates to a surface treatment agent that is applied to a surface formed of a polyamide resin to improve the adhesiveness of the surface.

Partial dentures (partial dentures) are often used as prosthetic restorations when some teeth are missing due to caries, accidents, or the like. This partial denture usually has a denture part in which an artificial tooth that replaces the missing tooth is fixed to the denture base (partial base) that covers the oral mucosa of the missing part, and a retaining device such as a clasp that is attached to the clasp made of the adjacent remaining natural tooth so that it does not come off. It may also have sub-connectors that connect it.

Metal materials are often used for the clasp from the viewpoints of strength and durability, but resin materials are sometimes used from the viewpoints of metal allergy countermeasures, aesthetics, wearing comfort, and the like. Partial dentures with clasps made of thermoplastic resin materials are also called non-metal clasp dentures (including cases that use no metal materials at all, as well as cases that use some metal materials such as metal rests and metal frames), and the demand for them is increasing due to the advantages described above. However, the current situation is that resin materials that can be used are limited from the viewpoint of various physical properties.

Polyamide resins (hereinafter sometimes abbreviated as PA resins) have been used since the 1950s as materials for clasps and bases of partial dentures because of their excellent feature of being resistant to breakage. However, since they do not adhere to acrylic resins, it is difficult to repair the inner surface of dentures with denture base relining materials (see Patent Document 1 and Non-Patent Document 1).

To supplement this point, since the human oral mucosa and jawbone gradually change, a gap often occurs between the denture and the oral mucosa within a few years. For this reason, it is necessary to perform regular repairs by applying a denture base lining material, which is a hardening material with plastic deformation properties, to the inner surface of the denture base that has caused poor fitting, filling the gaps, and then hardening the denture base to make it fit again. Conventional denture bases are mostly composed of (meth)acrylic resins or metal materials with good adhesive properties, and (meth)acrylic resin-based or silicone rubber-based materials (hardening materials of which are made of these materials) are widely used as the denture base lining material. However, in non-metal clasp dentures, the clasp and (denture) base are often integrally molded using the same thermoplastic resin from the viewpoint of productivity, and when PA resin with poor adhesion is used as the thermoplastic resin, restoration using these general denture base lining materials becomes difficult.

The following techniques are known for improving the adhesiveness of PA resin. That is, Patent Document 1 discloses, as an adhesive for a denture base lining material that enables a denture base lining material made of a (meth)acrylic resin or silicone rubber to be easily and strongly adhered to a denture made of a polyamide resin, "an adhesive for a denture base lining material for a denture base made of a polyamide resin, wherein an adhesive component for a curable composition constituting the denture base is an organic solution dissolved in a phenolic solvent and/or a fluoroalcoholic solvent."

In addition, Patent Document 2 describes "a polyamide resin denture base primer composition for bonding a polyamide resin denture base and a resin lining material attached to the back surface thereof, comprising 3 to 30% by weight of a thermoplastic resin for bonding, hexafluoroisopropanol (hereinafter sometimes simply referred to as "HFIP") as a first solvent that dissolves a part of the polyamide resin of the denture base, and a second solvent that dissolves the thermoplastic resin for bonding and is compatible with HFIP. Polyamide resin primer composition for denture base, characterized in that it consists of a mixed solvent of 97 to 70% by weight, and the mixed solvent is contained in a ratio of 70 to 10 of the first solvent to 30 to 90 of the second solvent, with the total amount being 100.

JP 2013-249297 A JP 2013-144648 A

Kenji Fueki et al., "Clinical application of partial dentures using thermoplastic resin (non-metal clasp dentures)," Journal of the Japanese Prosthodontic Society, Vol. 5, No. 4, pp. 387-408, 2013 Practical Plastic Encyclopedia Editing Committee "Practical Plastic Encyclopedia" Published by Sangyo Chokenkai Encyclopedia Publishing Center, May 1, 1993, p. 327

However, the phenolic solvent and/or fluoroalcoholic solvent used as the solvent in the adhesive for the backing material of Patent Document 1, and the hexafluoroisopropanol (HFIP) used as the first solvent of the primer composition of Patent Document 2 are not only biohazardous but also volatile liquids that emit a strong odor.

Therefore, an object of the present invention is to provide a surface treatment agent that improves the adhesiveness of PA resin and has excellent handleability such as low harm to the human body, low volatility, and no irritating odor.

The present inventors have completed the present invention as a result of intensive studies to solve the above problems.

That is, the first invention is a surface treatment agent for improving the adhesion between the adhesive surface of an article having an adhesive surface made of a polyamide resin and an adherend, the agent comprising a polyamide resin-insoluble non-basic organic solvent., benzenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid and at least one selected from the group consisting of paratoluenesulfonic acidOrganic sulfonic acid compoundand at least one anionic surfactant selected from the group consisting of sodium 1-octanesulfonate, sodium 1-decanesulfonate, sodium 1-dodecanesulfonate, sodium 1-hexadecanesulfonate and sodium 1-dodecylbenzenesulfonateThe surface treatment agent is characterized by containing a solution in which is dissolved.

The solution in the surface treatment agent of the present invention is preferably a solution obtained by dissolving an organic sulfonic acid compound at a concentration of 0.0001 (mmol/ml) or more and 5.0 (mmol/ml) or less with respect to 1 (ml) of the organic solvent. Moreover, it is preferable that the article is a denture or a denture base, and the adherent is a (meth)acrylate-based relining material and/or a silicone-based relining material. The lining material is obtained by curing a curable composition so that the cured product forms part of the denture base (repair part), and the lining material before curing is sometimes called the lining material. The adhesive strength that is practically required for the backing material is the adhesive strength with the cured body.

A second aspect of the present invention is a denture manufacturing method comprising the following steps: a treatment step of applying the surface treatment agent of the first aspect of the present invention to the adhesive surface of a denture base having an adhesive surface made of a polyamide resin; a removal step of removing the surface treatment agent after the treatment;

By using the surface treatment agent of the present invention, it is possible to improve the adhesiveness of the PA resin without using a substance that requires careful handling from the viewpoint of harm to the human body, odor, and the like. For example, even if the denture base of a denture (including a partial denture) that requires regular maintenance (repair for reconformation) using a lining material is made of PA resin, the surface treatment agent of the present invention can be used to safely and easily repair (in the same manner as conventional repairs, except for the treatment using the surface treatment agent of the present invention).

The reason why such an effect is obtained is not necessarily clear, but when the surface of the PA resin to which the surface treatment agent of the present invention is applied is observed with a laser microscope, the surface becomes uneven and uneven. That is, when the organic sulfonic acid compound acts on the PA resin, the polymer chains thereof are partially cleaved to form an oligomer, and dissolution progresses unevenly on the surface such that the oligomer dissolves in an organic solvent. As a result, the surface is roughened, and the curable composition adheres to the roughened surface (the curable composition also penetrates into recesses having undercuts). After that, it is presumed that the adhesive strength is improved by the anchor effect caused by the fixation in the state of being fitted into the recesses of the roughened surface by curing.

It is known that aqueous solutions of inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid and acetic acid attack PA resin (see Non-Patent Document 2), but it is not known that organic solvent solutions of organic sulfonic acid compounds have such effects.

The surface-treating agent of the present invention is a surface-treating agent for improving the adhesiveness between the adhesive surface of an article having an adhesive surface made of a polyamide resin and an adherend, and is characterized by comprising a solution of an organic sulfonic acid compound dissolved in a non-basic organic solvent that does not dissolve the polyamide resin.

The article to be treated with the surface treatment agent of the present invention is not particularly limited as long as the surface of the adhesion surface, which is the surface for adhering the adherend, is composed of a polyamide resin, but the adhesiveness improvement effect by using the surface treatment agent of the present invention is high. It is preferable that a solid member finally adhered (bonded) to the adhesive surface is formed by curing the adhesive after curing. A pasty curable composition containing a polymerizable monomer, a filler and a polymerization initiator can be suitably used as such an "adhesive". The "adhesive" made of such a curable composition may be used as an adhesive to adhere a secondary "adhesive" made of a solid material (a solid material such as a metal material or a resin material). Further, a material made of a thermoplastic resin can also be used as the "adhesive". In this case, the molten resin is applied to an adhesive surface treated with the surface treatment agent of the present invention in a molten state, and then cooled and hardened, whereby the molten resin penetrates into recesses having undercuts and is then hardened, so that the adhesiveness can be improved by the anchor effect.

From the viewpoint of usefulness of the surface treatment agent of the present invention, it is preferable that the article is a denture or a denture base, and the adhesive is a (meth)acrylate-based relining material and/or a silicone-based relining material.

The polyamide resin (PA resin) constituting the surface of the adhesive surface of the article to be treated with the surface treatment agent of the present invention is not particularly limited as long as it is a resin composed of a polymer or copolymer having a structure in which a large number of monomers are bonded by amide bonds. Specific examples of such polyamide resins include nylon 6 (ring-opening polycondensate of ε-caprolactam), nylon 11 (ring-opening polycondensate of undecane lactam), nylon 12 (ring-opening polycondensate of lauryllactam), nylon 66 (condensation polymer of adipic acid and hexamethylenediamine), nylon 610 (condensation polymer of sebacic acid and hexamethylenediamine), and nylon 612 (1,12-dodecanedioic acid and hexamethylenediamine). MXD6 (condensation product of adipic acid and metaxylenediamine), Nylon 6T (condensation product of terephthalic acid and hexamethylenediamine), Nylon 6I (polycondensation product of isophthalic acid and hexamethylenediamine), Nylon 9T (polycondensation product of terephthalic acid and nandiamine), and aromatic polyamides such as Nylon M5T (polycondensation product of terephthalic acid and methylpentadiamine). These may be used alone or in combination of two or more. When the surface treatment agent of the present invention is used to improve adhesion to a denture base material, nylon 12 is preferably used as the polyamide resin because it is often used as a denture base material.

The organic solvent, which is the main component of the surface treatment agent of the present invention, is considered to have the function of dissolving and diluting the organic sulfonic acid compound and the function of liberating and dissolving the residue of the PA resin whose bond has been cleaved by the organic sulfonic acid compound. The organic solvent used in the present invention should be insoluble in the polyamide resin and non-basic. By having no solubility in the polyamide resin, it is possible to reduce harm to the human body and difficulty in handling. In addition, by being non-basic, it is possible to exhibit excellent surface roughening ability without lowering the function of the organic sulfonic acid compound, which is the active ingredient.

Here, the polyamide resin insolubility means that the solubility in the polyamide resin constituting the adhesive surface at 20° C. is 0.1 (g/100 g-solvent) or less, preferably 0.05 (g/100 g-solvent) or less, particularly preferably 0.001 (g/100 g-solvent) or less. In addition, non-basic means that it does not reduce the acidity of organic sulfonic acid compounds, and non-basic organic solvents include amides such as hexamethylphosphoric acid triamide (HMPA), N-methylpyrrolidone (NMP), N-cyclohexylpyrrolidone (NCP), N-methylcaprolactam, tetramethylurea (TMU), dimethylformamide (DMF) and dimethylacetamide (DMA); It means that it is an organic solvent that is not a basic organic solvent such as

Examples of non-basic organic solvents insoluble in polyamide resin include (1) alkanes such as hexane, n-heptane and n-octane; (2) cycloalkanes such as cyclohexane, cycloheptane and cyclooctane; (4) Ethers such as diethyl ether, ethyl propyl ether, tetrahydrofuran, dioxane; (5) Esters such as ethyl acetate, propyl acetate, isopropyl acetate, amyl acetate, butyl acetate, isobutyl acetate, methyl formate, methyl butyrate, ethyl propionate; (6) acetone, methyl ethyl ketone, methyl propyl ketone, methyl Ketones such as isopropyl ketone; (7) Cyclic ketones such as cyclohexanone, cycloheptanone, and cyclooctanone; (8) Aromatics such as benzene, toluene, p-xylene, amylbenzene, and ethylbenzene; (9) Organic chlorine compounds such as carbon tetrachloride, dichloromethane, trichloroethane, tetrachloroethane, and chloroform; and the like can be exemplified. These organic solvents may be used alone or in combination of two or more.

Among these, organic solvents such as hexane, toluene, ethyl acetate, chloroform, dichloromethane, acetone, acetonitrile, methanol, ethanol, and IPA are preferably used because of their high effectiveness. In addition, it is preferable to use ethyl acetate, dichloromethane, ethanol, IPA, etc., which are commonly used in the field of dental materials, because they are less biotoxic and have good storage stability when the organic sulfonic acid compound is dissolved.

The organic sulfonic acid compound used in the present invention means a sulfonic acid compound that has an organic group composed of an element selected from the group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, phosphorus, and halogen elements and does not contain silicon and metal elements. Aromatic sulfonic acids and aliphatic sulfonic acids can be suitably used as such organic sulfonic acid compounds.

Specific examples of aromatic sulfonic acids that can be preferably used include benzenesulfonic acid, n-butylbenzenesulfonic acid, n-octylbenzenesulfonic acid, n-dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2,5-dibutylbenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 5-amino-2-methylbenzenesulfonic acid, 3,5-diamino-2, 4,6-trimethylbenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, p-phenolsulfonic acid, cumenesulfonic acid, xylenesulfonic acid, o-cresolsulfonic acid, m-cresolsulfonic acid, p-cresolsulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, 1-naphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, dino Nilnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 4,4-biphenyldisulfonic acid, anthraquinone-2-sulfonic acid, m-benzenedisulfonic acid, 2,5-diamino-1,3-benzenedisulfonic acid, aniline-2,4-disulfonic acid, anthraquinone-1,5-disulfonic acid, polystyrenesulfonic acid, and the like.

Specific examples of aliphatic sulfonic acids that can be preferably used include aliphatic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, n-octylsulfonic acid, pentadecylsulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, 1,2-ethanedisulfonic acid, 1,3-propanedisulfonic acid, aminomethanesulfonic acid, and 2-aminoethanesulfonic acid, cyclopentanesulfonic acid, cyclohexanesulfonic acid and camphorsulfonic acid, and 3-cyclohexylaminopropane. Sulfonic acid and the like can be mentioned.

Among these, in the present invention , at least one selected from the group consisting of benzenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, and p-toluenesulfonic acid is used from the viewpoint of solubility in the organic solvent and high roughening effect .

The concentration of the organic sulfonic acid compound in the solution constituting the surface treatment agent of the present invention may be less than the saturation concentration of the organic sulfonic acid compound, but it is usually a concentration in which the amount of the dissolved organic sulfonic acid compound is in the range of 0.0001 to 5.0 (mmol/ml), expressed in terms of the amount (mmol: mmol) of the dissolved organic sulfonic acid compound with respect to 1 (milliliter: ml) of the "polyamide resin-insoluble non-basic organic solvent". The concentration is preferably 0.001 to 3.0 (mmol/ml), particularly 0.005 to 2.5 (mmol/ml), because a low concentration makes it difficult to obtain a high adhesive strength due to a low roughening effect, and a high concentration causes a large amount of generated oligomers to remain on the surface and easily cause adhesion inhibition.

By adding an anionic surfactant to the surface treatment agent of the present invention, the concentration adjustment range of the organic sulfonic acid compound can be widened. For example, when benzenesulfonic acid having an octanol/water partition coefficient of −1.2 is used as an organic sulfonic acid compound, benzenesulfonic acid cannot be dissolved in a hydrophobic solvent such as toluene (octanol/water partition coefficient is 2.69) or hexane (octanol/water partition coefficient is 3.9), but by adding an anionic surfactant, benzenesulfonic acid can be dissolved in toluene or hexane.

The anionic surfactant may be appropriately selected according to the combination of the organic sulfonic acid compound and organic solvent used. Examples of anionic surfactants that can be suitably used include alkali metal or alkaline earth metal salts of alkylsulfonic acids, allylsulfonic acids, alpha-olefinsulfonic acids, arylsulfonic acids, alkylarylsulfonic acids and alkylarylpolyethersulfonic acids, sulfosuccinic acids, alkyl esters of sulfosuccinic acid, dialkyl esters of sulfosuccinic acid; alkylaryl esters of sulfosuccinic acid and polyoxyethylene alkylaryl esters of sulfosuccinic acid; alkali metal salts or alkaline earth metal salts of esters of; alkali metal salts or alkaline earth metal salts of alkylaryl esters of sulfuric acid, phosphoric acid and sulfoacetic acid; and the like. In the present invention, among these, anionic surfactants having a large number of carbon atoms in straight-chain alkyl groups such as sodium 1-octane sulfonate, sodium 1-decane sulfonate, sodium 1-dodecane sulfonate, sodium 1-hexadecane sulfonate, and sodium 1-dodecylbenzene sulfonate are used from the viewpoint that effects can be easily obtained with a small amount . The amount of the anionic surfactant to be added may be appropriately determined according to the combination of the organic sulfonic acid compound and the organic solvent, but from the viewpoint of the effect and prevention of overuse, it is usually determined with a guideline of about twice the critical micelle concentration of the anionic surfactant to be used. When the anionic surfactant is added, the amount (mmol) to be dissolved in 1 (ml) of the organic solvent is usually 0.001 to 1 (mmol/ml), preferably 0.005 to 0.5 (mmol/ml).

The surface treatment agent of the present invention may consist of the above solution alone, but may contain a thickener for the purpose of improving the coating properties and suppressing outflow from the surface to be treated (contact surface). To give an example of a thickener that can be suitably used, any component can be added to the surface treating agent of the present invention within a range that does not impair the effects of the present invention. For example, thickening agents can include cellulose, derivatized cellulose, hydroxypropyl cellulose, hydrophobic and/or hydrophilic fumed silica, silicone elastomers, silicone elastomer blends, carboxypolymethylene; polyacrylic polymers and/or copolymers, cellulose ethers, methacrylates, copolymers of methyl vinyl ether and maleic anhydride, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, polyvinyl alkyl ether-maleic acid copolymers, carboxyvinyl polymers, proteins, sorbitan esters, sucrose, and the like. The amount of the thickening agent added is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the solution.

Further, other components such as pigments, dyes and stabilizers can be added as long as the effects of the invention are not impaired.

When the adhesive surface of the article is treated with the surface treatment agent of the present invention, the adhesive surface is cleaned in advance by a method such as washing with an organic solvent such as water or alcohol that does not attack the adhesive surface, and if necessary, after drying treatment, an appropriate amount of the surface treatment agent of the present invention is dropped using, for example, a dropper, and if necessary, it is spread and brought into good contact with the surface for several tens of seconds to several minutes, and then wiped off with a cloth or paper. The surface may be cleaned and dried before bonding to the adherend. When using a "curable composition having plastic deformation property" such as a backing agent as the adhesive, the curable composition may be placed on the adhesive surface (pre-treated adhesive surface) treated with a surface treatment agent, and if necessary, subjected to shaping treatment and then cured. Further, when the curable composition is used as an adhesive, the curable composition is applied to the already treated adhesive surface, and a secondary "adhesive" made of a solid material (a solid material such as a metal material or a resin material) is placed thereon, and then the adhesive (curable composition) is cured to perform adhesion.

By using the pretreatment agent of the present invention, it is possible to easily produce a denture base made of a polyamide resin or a denture using the same, which is adapted using a lining material. That is, a denture base made of polyamide resin or a denture using the same can be easily manufactured by a method comprising a treatment step of applying the surface treatment agent of the present invention to the adhesive surface of a denture base having an adhesive surface made of a polyamide resin, a removal step of removing the surface treatment agent after the treatment, and a lining step of building up a lining material on the adhesive surface after the removal step, shaping the lining material, and curing the lining material.

At this time, the lining material may be appropriately selected from among conventionally known materials depending on the purpose of use. Examples of such a backing material include poly(meth)acrylate resin, polyolefin resin, polyamide resin, polyester resin, polyether resin, polynitrile resin, polyvinyl resin, cellulose resin, fluororesin, imide resin, and silicone resin.

For example, when the patient himself/herself performs treatment and uses it for a relatively short period of one to several days, a lining material that is a powdery, creamy, or seal-like adhesive for fixing the denture base (so-called denture stabilizer) can be selected. As the lining material, it is also possible to select a dental mucous membrane conditioning material, a soft lining material, and a hard lining material that are applied by a dentist. When the oral mucosa has an ulcer or inflammation and is used until the oral mucosa is restored to a healthy state while relieving pain, a relining material (dental mucous membrane conditioning material and soft relining material) with a durometer A hardness of 55 or less can be selected. A dental mucous membrane conditioner is usually used for one to several weeks, and a soft relining material is used for a long period of 6 months or more. The physical properties of both dental mucous membrane conditioners and soft relining materials are defined by JIS standards. Furthermore, if it is desired to bond more firmly and improve durability, a hard relining material having a Knoop hardness of 7Hk or more (JIST6521 (hard relining material for denture base)) can be selected.

EXAMPLES Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be given, but the present invention is not limited to these. First, various compounds and materials used in the experiments are shown below.

[Organic solvent]
<Non-basic organic solvent insoluble in polyamide resin>
・Methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・ Acetonitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・ Ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Acetone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・ Isopropyl alcohol (IPA: manufactured by Tokuyama Corporation)
・ Ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Dichloromethane (manufactured by Tokuyama Corporation)
・Chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
<Polyamide resin-soluble organic solvent>
・ Hexafluoroisopropanol (HFIP: manufactured by Tokyo Chemical Industry Co., Ltd.)
<Basic organic solvent>
・Dimethylformamide (DMF: manufactured by Tokyo Chemical Industry Co., Ltd.)
<Non-organic solvent>
- Purified water (water: manufactured by Nichi-Iko Co., Ltd.).

[Organic sulfonic acid compound]
・ A: Dodecylbenzenesulfonic acid (brown liquid, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ B: benzenesulfonic acid (white solid, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ C: methanesulfonic acid (colorless transparent liquid, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ D: ethanesulfonic acid (brown transparent liquid, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ E: 4-hydroxybenzenesulfonic acid (white solid, manufactured by Tokyo Chemical Industry Co., Ltd.)
· F: paratoluenesulfonic acid (white solid, manufactured by Tokyo Chemical Industry Co., Ltd.).

[Anionic surfactant]
・ G: Sodium 1-octane sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ H: Sodium 1-decanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ I: Sodium 1-dodecanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ J: Sodium 1-hexadecanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.)
· K: Sodium 1-dodecylbenzenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.).

[Lining material]
<(Meth)acrylate hard lining material>
・ W: Tokuso Light Rebase <Pink> (Photopolymerization, manufactured by Tokuyama Dental Co., Ltd.)
・X: Tokuyama Rebase III <Normal, Pink> (Chemical polymerization, manufactured by Tokuyama Dental Co., Ltd.)
・ Y: Tokuyama Rebase II <Normal, Pink> (Chemical polymerization, manufactured by Tokuyama Dental Co., Ltd.)
・ Z: Clari Base <Normal, Pink> (Chemical polymerization, manufactured by Kuraray Noritake Dental Co., Ltd.)
<Silicone-based soft lining material>
・S: Soft Liner Tough <Medium> (manufactured by Tokuyama Dental Co., Ltd.).

Next, a method for evaluating the surface treatment agent will be described.
1. Evaluation of handling properties Various organic sulfonic acid compounds, HFIP, hydrochloric acid, sulfuric acid, formic acid, acetic acid, and methacrylic acid, which are solutes, were evaluated for their odor during handling.

2. Evaluation of Solubility In order to evaluate the dissolution acceleration hardening of the organic sulfonic acid compound in the organic solvent by the anionic surfactant, the organic sulfonic acid compound, the organic solvent, and the anionic surfactant added as necessary were mixed in a predetermined composition, and the dissolved state of the organic sulfonic acid compound was visually evaluated. When completely dissolved in the organic solvent, it was evaluated as ◯.

3. Evaluation of adhesive strength 3-1. Preparation of Adherend PA resin Nylon 12 (trade name: Valplast, manufactured by Unival Co., Ltd.) was molded into a plate of 1 cm square and 0.5 cm thick, and polished with #800 waterproof abrasive paper to prepare an adherend.

3-2. Evaluation of Adhesion to (Meth)Acrylate-Based Hard Lining Material 0.1 (ml) of the surface treatment agent was dropped on the surface of the adherend with a dropper and left for 60 seconds. After 60 seconds, the surface treatment agent was wiped off with a paper cloth (manufactured by Nippon Paper Crecia Co., Ltd.) impregnated with ethanol. A double-sided tape having a 3 mm diameter hole was attached to define the adhesion area, and a 0.5 mm thick paraffin wax having a 8 mm diameter hole was attached so as to be concentric with the 3 mm diameter hole to form a simulated repair portion. After that, the simulated repair portion was filled with a dough-like material obtained by kneading the powder and liquid of the (meth)acrylate hard lining material at the kneading ratio specified by the manufacturer, and then lightly pressed with a polypropylene film from above. When Toxo Light Rebase was used for the (meth)acrylate-based hard lining material, after filling, the material was allowed to stand in a wet environment at 37°C for 5 minutes, and then irradiated with light for 5 minutes using an LED polymerizer for dental laboratory α Light V (manufactured by Morita Co., Ltd.). When chemically polymerized Tokuyama maribase III, Tokuyama maribase II, or Kuraribase was used as the (meth)acrylate hard lining material, the material was allowed to stand at 37° C. in a humid environment for 1 hour. After that, the test piece was immersed in water at 37°C for 24 hours. A metal attachment used in a tensile test was adhered onto the (meth)acrylate hard backing material of the taken-out test piece. The tensile strength was measured by setting the test piece in a precision universal testing machine (AG-Xplus 50 kN, manufactured by Shimadzu Corporation) at a crosshead speed of 2 mm/min. In the test, five measurements were performed for one sample, and the average value was taken as the tensile strength.

3-3. Evaluation of Adhesion to Adherend and Silicone-Based Soft Lining Material 0.1 (ml) of the surface treatment agent was dropped on the surfaces of the two adherends using a dropper and left for 60 seconds. After 60 seconds, the surface treatment agent was wiped off with a paper cloth (manufactured by Nippon Paper Crecia Co., Ltd.) impregnated with ethanol. The adhesion primer attached to Sofly Liner Tough <Medium> was applied to the surface-modified side of the two adherends with a disposable brush. After that, a fluororesin (polytetrafluoroethylene) mold having a thickness of 3 mm and a hole having a diameter of 10 mm was placed on one of the adherends to form a simulated repair portion. Sofly Liner Tough, which is a silicone-based soft lining material, was kneaded with a mixing tip, filled in the simulated repair portion, and then placed on top of it so that the surface-modified side of another adherend was in contact with the lining material and pressed. After being left for 1 hour in a 37° C. wet environment, the test piece was immersed in water at 37° C. for 24 hours. Metallic attachments used in the tensile test were adhered to the upper and lower sides of the specimen taken out, that is, to both back sides of the adherend. The tensile strength was measured by setting the test piece in a precision universal testing machine (AG-Xplus 50 kN, manufactured by Shimadzu Corporation) and performing a tensile test on both sides of the metal attachment at a crosshead speed of 5 mm/min. In the test, five measurements were performed for one sample, and the average value was taken as the tensile strength.

Example 1
As an organic sulfonic acid compound, 0.10 g of dodecylbenzenesulfonic acid was dissolved in 1 (ml) of ethyl acetate, which is a non-basic organic solvent that does not dissolve polyamide resin, to prepare a surface treatment agent with a concentration of 0.3 (mmol/ml). Next, evaluation of adhesiveness to (meth)acrylate hard backing material and evaluation of handleability were carried out using Toxo Light Rebase. As a result, the tensile strength was 10.1 MPa, and the handleability was ◯.

Examples 2-27
Preparation of the surface treatment agent and evaluation of handleability were carried out in the same manner as in Example 1 except that the non-basic organic solvent insoluble in the polyamide resin, the organic sulfonic acid compound and its concentration were as shown in Table 1. Adhesion was also evaluated in the same manner except that the material shown in Table 1 was used as the backing material. Table 1 shows the results.

Comparative example 1
Direct adhesion evaluation was performed without treating the adherend with a surface treatment agent, and the tensile strength was as low as 2.1 MPa.

Comparative example 2
A surface treatment agent having a concentration of 1.0 (mmol/ml) was prepared by dissolving 0.17 g of HFIP as a solute in 1 (ml) of ethyl acetate, which is a non-basic organic solvent that does not dissolve polyamide resin. Next, evaluation of adhesiveness to (meth)acrylate hard backing material and evaluation of handleability were carried out using Toxo Light Rebase. As a result, the tensile strength was 2.6 MPa, and the handleability was x.

Comparative Examples 3-14
A surface treatment agent was prepared in the same manner as in Comparative Example 2 except that the type of non-basic organic solvent insoluble in the polyamide resin and the concentration of HFIP were changed as shown in Table 2, and the handling property was evaluated. Table 2 shows the results.

Comparative example 15
This is an example using a surface treatment agent consisting only of HFIP without using a polyamide resin-insoluble non-basic organic solvent and an organic sulfonic acid compound. Although the surface of the adherend was roughened, a large amount of oligomer was formed on the surface, remained on the surface of the adherend and became an adhesion hindrance factor, and the tensile strength to the (meth)acrylate hard backing material was a low value of 2.8 MPa.

Comparative Examples 16-20
Preparation of the surface treatment agent and evaluation of handleability were carried out in the same manner as in Comparative Example 2, except that the type and concentration of the solute used and the type of solvent used were as shown in Table 2. Table 2 shows the results. The handleability was x because of the irritating odors of hydrochloric acid, sulfuric acid, formic acid, acetic acid, and methacrylic acid.

Comparative example 21
This is an example of using a surface treatment agent consisting only of liquid dodecylbenzenesulfonic acid without using a non-basic organic solvent insoluble in polyamide resin. Next, evaluation of adhesiveness to (meth)acrylate hard backing materials and evaluation of handling properties were performed using Toxo Light Rebase. As a result, the tensile strength was 2.6 MPa, and the handleability was x.

Comparative example 22
In this example, 0.16 g of benzenesulfonic acid was dissolved as a solute in 1 (ml) of water, which is a non-organic solvent, to prepare a surface treatment agent having a concentration of 1.0 (mmol/ml). As a result, the adhesion strength was as low as 2.1 MPa. In addition, the handleability was ○.

Comparative example 23
In this example, 0.03 g of dodecylbenzenesulfonic acid, which is an organic sulfonic acid, was dissolved in 1 (ml) of dimethylformamide, which is a basic organic solvent, to prepare a surface treatment agent having a concentration of 0.1 (mmol/ml). As a result, the effect of the organic sulfonic acid was lost, and the adhesive strength was as low as 2.0 MPa. In addition, the handleability was ○.

Example 28
As an organic sulfonic acid compound, 0.016 g of benzenesulfonic acid and 0.065 g of sodium 1-octanesulfonate, which is an anionic surfactant, were dissolved in 1 (ml) of toluene, which is a non-basic organic solvent insoluble in polyamide resin, to prepare a surface treatment agent. At this time, the concentration of benzenesulfonic acid is 0.1 (mmol/ml) and the concentration of sodium 1-octanesulfonate is 0.3 (mmol/ml). Next, using Toxo Light Rebase, the adhesiveness and solubility to (meth)acrylate hard backing materials were evaluated. As a result, the tensile strength was 9.1 MPa, and the solubility was ◯.

Examples 29-34
A surface treatment agent was prepared in the same manner as in Example 25 except that the type of non-basic organic solvent insoluble in the polyamide resin and the type and concentration of the anionic surfactant were shown in Table 3, and adhesion and solubility were evaluated. Table 3 shows the results.

Comparative Examples 24-25
As an organic sulfonic acid compound, 0.016 g of benzenesulfonic acid was added to 1 (ml) of toluene or 1 (ml) of hexane, which is a non-basic organic solvent that does not dissolve the polyamide resin, to prepare a surface treatment agent with a theoretical concentration of 0.1 (mmol/ml). At this time, benzenesulfonic acid was not dissolved in toluene or hexane, and the solubility was x. Table 3 shows the results of evaluation of adhesion to (meth)acrylate hard backing materials using Toxo Light Rebase. The adhesion strength was low because the effect of benzenesulfonic acid was not obtained.

Example 35
As an organic sulfonic acid compound, 0.033 g of dodecylbenzenesulfonic acid was dissolved in 1 (ml) of ethyl acetate, which is a non-basic organic solvent that does not dissolve polyamide resin, to prepare a surface treatment agent with a concentration of 0.1 (mmol/ml). Next, evaluation of adhesiveness to a silicone-based soft backing material was performed using a soft liner tough. As a result, the tensile strength was 1.2 MPa.

Examples 36-40
Preparation of the surface treatment agent and adhesion evaluation were performed in the same manner as in Example 35 except that the type of non-basic organic solvent insoluble in the polyamide resin and the concentration of the organic sulfonic acid compound were as shown in Table 4. Table 4 shows the results.

Comparative example 26
In this example, no surface treatment agent was used, pretreatment was performed only with the adhesive primer attached to Sofly Liner Tough <Medium>, and the adhesion to a silicone-based soft backing material was evaluated using Sofly Liner Tough <Medium>. The result was a very low adhesive strength of 0.04 MPa.

Comparative Examples 27-28
A surface treatment agent having a concentration of 0.1 (mmol/ml) was prepared by dissolving 0.017 g of HFIP in 1 (ml) of ethyl acetate or chloroform, which is a non-basic organic solvent that does not dissolve polyamide resin. Next, the adhesion to the silicone-based soft backing material was evaluated using a soft liner tough. Table 4 shows the results.

Claims (4)

A surface treatment agent for improving the adhesion between the adhesive surface of an article having an adhesive surface made of a polyamide resin and an adherend, the agent being added to a non-basic organic solvent insoluble in the polyamide resin., benzenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid and at least one selected from the group consisting of paratoluenesulfonic acidOrganic sulfonic acid compoundand at least one anionic surfactant selected from the group consisting of sodium 1-octanesulfonate, sodium 1-decanesulfonate, sodium 1-dodecanesulfonate, sodium 1-hexadecanesulfonate and sodium 1-dodecylbenzenesulfonateThe surface treatment agent, characterized in that it contains a solution in which is dissolved. 2. The surface treating agent according to claim 1, wherein the concentration of the organic sulfonic acid compound in the solution is equal to or lower than the saturation concentration of the organic sulfonic acid compound and is 0.0001 (mmol/ml) or more and 5.0 (mmol/ml) or less. The surface treatment agent according to claim 1 or 2 , wherein the article is a denture or a denture base, and the adhesive is a (meth)acrylate relining material and/or a silicone relining material. A treatment step of applying the surface treatment agent according to claim 1 to the adhesive surface of a denture base having an adhesive surface made of a polyamide resin,
A method for manufacturing a denture, comprising a removing step of removing the surface treatment agent after the treatment, and a lining step of building up a ( meth)acrylate-based lining material and/or a silicone-based lining material on the adhesive surface after the removing step, shaping the lining material, and then curing the lining material.