JP2023155627A - Molding material and method for producing article - Google Patents

Abstract

To provide a molding material that is easy to produce industrially and exhibits superior moldability, resulting in a molding with superior coating adhesion.SOLUTION: A molding material includes (1) a resin and (2) a compound A that includes a hydrocarbon group with two or more carbon atoms and an amino group in one molecule, wherein the compound A is solid at 25°C. The molding material is preferably used to produce a molding in an article, wherein the article consists of the molding, and a coating formed on at least part of the surface of the molding.SELECTED DRAWING: None

Description

The present invention relates to a molding material and a method for manufacturing an article.

Molding materials (specifically, molding materials that contain resin and are molded by heating) are used in a wide range of fields such as electrical and electronic fields, home appliances, automobiles, building materials, housing equipment, and miscellaneous goods. ing.

For example, Patent Document 1 describes a molding material for molded products that comes into contact with water, which contains 1 to 50 parts by weight of a polymeric antistatic agent based on 100 parts by weight of a styrene resin.

Japanese Patent Application Publication No. 2005-248138

Molding materials containing resin are usually manufactured as powdered or granular molding materials through kneading and pulverization of raw materials. Then, a molded article is manufactured by an appropriate molding method using the molding material thus manufactured. An example of the molding method is an injection molding method in which a molding material melted by heat is injected into a mold.

Manufactured molded products may be subjected to some processing or post-processing.
For example, for the purpose of improving design or for other purposes, paint may be applied to the surface of a manufactured molded article to form a coating film. In this case, it is preferable that the coating film strongly adheres to the molded article.

However, another problem may arise when trying to improve the adhesion of the coating on a molded article.
Specifically, in order to create a molding material that can produce molded products with good coating adhesion, it is necessary to reduce the amount of mold release agent added to the raw materials. There is a concern that raw materials tend to adhere to a kneading device (typically a kneading roll), that is, it becomes difficult to industrially manufacture a molding material. In addition, molding materials that can produce molded products with good paint film adhesion have low fluidity due to friction with the inner wall of the molding machine during injection molding, and hardening of the molding material progresses due to shear heat generation. There is a concern that it will be difficult to perform injection from an injection molding machine. In other words, a molding material that adheres well to the coating film when it is made into a molded product has the flip side of this, but it also tends to adhere to the kneading equipment during the production of the molding material, is difficult to fill into the mold cavity during molding, and adheres to the mold. There is a concern that moldability may deteriorate due to easier molding.
In short, there is a balance between "increasing paint film adhesion" of molded products and "industrial ease of manufacturing" and "industrial moldability" of the molding material used to manufacture molded products. There are concerns that are difficult to address.

The present invention has been made in view of these circumstances.
One of the objects of the present invention is to provide a molding material that is easy to manufacture industrially, has good moldability, and has good coating film adhesion of the resulting molded product.

The present inventors completed the invention provided below and solved the above problems.

The present invention is a method for manufacturing the following molding material and article.

1.
resin and
A compound A having a hydrocarbon group having 2 or more carbon atoms and an amino group in one molecule,
A molding material that is solid at 25°C.
2.
1. The molding material described in
A molding material in which the number of carbon atoms in the hydrocarbon group is 30 or less.
3.
1. or 2. The molding material described in
A molding material in which the compound A contains at least one selected from the group consisting of ethylenediamine, laurylamine, behenylamine, oleylpropylenediamine, and behenylpropylenediamine.
4.
1. ~3. The molding material according to any one of
A molding material in which the content of the compound A is 1 to 5% by mass.
5.
1. ~4. The molding material according to any one of
A molding material in which the resin includes a phenolic resin.
6.
1. ~5. The molding material according to any one of
Furthermore, molding materials containing curing aids.
7.
1. ~6. The molding material according to any one of
Molding materials that also contain fillers.
8.
1. ~7. The molding material according to any one of
A molding material that also contains a mold release agent.
9.
1. ~8. The molding material according to any one of
A molding material used for manufacturing a molded article, which includes a molded article and a coating film formed on at least a portion of the surface of the molded article.
10.
1. ~9. A molding step of manufacturing a molded article using the molding material described in any one of
a coating film forming step of forming a coating film on at least a portion of the surface of the molded article using a paint;
A method of manufacturing an article, including:

ADVANTAGE OF THE INVENTION According to this invention, the molding material which is easy to manufacture industrially, has good moldability, and has good coating film adhesion of the molded article obtained is provided.

Embodiments of the present invention will be described in detail below.
In the present specification, the notation "X to Y" in the description of numerical ranges refers to not less than X and not more than Y, unless otherwise specified. For example, "1 to 5% by mass" means "1 to 5% by mass".

In the description of a group (atomic group) in this specification, a description that does not indicate whether it is substituted or unsubstituted includes both those without a substituent and those with a substituent. For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The term "organic group" as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.

<Molding material>
The molding material of this embodiment includes a resin, a compound A having a hydrocarbon group having 2 or more carbon atoms, and an amino group in one molecule.
Moreover, the molding material of this embodiment is solid at 25°C. Specifically, the molding material of this embodiment is solid at 25° C. (normal temperature), and is used to melt by heating to obtain a molded product of a desired shape.

In order to solve the above-mentioned problems, the present inventors investigated adding various candidate compounds to the molding material.
As a result of the study, it was decided to add Compound A, which has a hydrocarbon group having two or more carbon atoms and an amino group in one molecule, to the molding material. This makes it difficult for the raw materials to adhere to the kneading equipment when kneading the raw materials for the molding material, and it is possible to obtain sufficient moldability of the molding material and to improve the adhesion with the coating film of the molded product. I found it.

This is just a guess, but (i) the action of the hydrocarbon group (low polarity) in Compound A suppresses the adhesion of raw materials to the kneading equipment, and also prevents the adhesion of raw materials to the inner wall of the molding machine and the mold during the production of molded products. It is believed that (ii) the action of the amino group (highly polar) in Compound A increases the adhesion to the coating film of the molded article.
Also, although this is just speculation, because Compound A has a hydrocarbon group with two or more carbon atoms, there is a possibility that it is likely to be unevenly distributed on the surface of the molded product during the production of the molded product (when the molding material is melted). There is. It is thought that the above-mentioned effects can be more easily obtained because Compound A is more likely to be unevenly distributed on the surface of the molded article. Further, it seems that even when the amount of Compound A used is relatively small, the above-mentioned effects can be easily obtained.

This embodiment will be described in more detail below.

(resin)
The resin contained in the molding material of this embodiment is not particularly limited. As the resin, thermosetting resins and thermoplastic resins known in the field of molding materials can be used as appropriate.

・Thermosetting resin As the thermosetting resin, for example, one or more selected from the group consisting of phenol resin, epoxy resin, phenoxy resin, cyanate resin, melamine resin, polyurethane, and unsaturated polyester resin. Can be mentioned.
Among these, phenol resins, epoxy resins, and phenoxy resins are preferred from the viewpoint of obtaining good mechanical properties and appropriately producing a molding material. These resins will be specifically explained below.

Specifically, a novolac type phenol resin, a resol type phenol resin, or a modified phenol resin can be used as the phenol resin.

The novolac type phenolic resin is not particularly limited as long as it is a resin obtained by reacting raw material phenols and aldehydes without a catalyst, in the presence of an acidic catalyst, or a transition metal catalyst.
Examples of novolac type phenolic resins include unmodified phenolic resins, cresol resins, resorcinol resins, xylenol resins, cresol/xylenol resins, cresol-modified phenolic resins, resorcinol-modified phenolic resins, xylenol-modified phenolic resins, and alkylphenol resins. , alkylphenol-modified phenolic resin, bisphenol-modified phenolic resin, cashew oil-modified phenolic resin, tall oil-modified phenolic resin, rosin-modified phenolic resin, terpene oil-modified phenolic resin, random novolac type phenolic resin, high ortho novolac type A phenol resin or a resin using one or more of the following phenols as raw materials can be used.

For example, novolac type phenolic resin is produced by mixing phenols and aldehydes, which are raw material monomers, in the absence of a catalyst or in the presence of a catalyst (for example, an acidic catalyst or a transition metal catalyst) at a molar ratio of aldehydes to phenols (aldehydes/phenol). ) can be obtained by controlling the reaction so that it is 0.5 to 1.0.

The raw material phenol is not particularly limited as long as it is a monomer having a phenolic hydroxyl group.
Specifically, phenol; dihydroxybenzenes such as o-dihydroxybenzene, m-dihydroxybenzene, and p-dihydroxybenzene; cresols such as o-cresol, m-cresol, and p-cresol; ethylphenol, butylphenol, octylphenol, nonylphenol, etc. Alkylphenol; Xylenol; Components contained in cashew oil such as 3-pentadecylphenol, 3-pentadecylphenol monoene, 3-pentadecylphenol diene, 3-pentadecylphenol triene; 1,3-dihydroxy-5-pentadecylbenzene , 1,3-dihydroxy-5-pentadecylbenzene monoene, 1,3-dihydroxy-5-pentadecylbenzenediene, 1,3-dihydroxy-5-pentadecylbenzentriene; 2-methyl-1 , 3-dihydroxy-5-pentadecylbenzene, 2-methyl-1,3-dihydroxy-5-pentadecylbenzene monoene, 2-methyl-1,3-dihydroxy-5-pentadecylbenzenediene, 2-methyl-1 , 3-dihydroxy-5-pentadecylbenzentriene; urushiol; bisphenol A; bisphenol F; bisphenol S.
Phenols can be used alone or in combination of two or more.

As the raw material aldehydes, known ones can be used as appropriate.
For example, aldehyde compounds such as formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, butyraldehyde, crotonaldehyde, benzaldehyde, and salicylaldehyde; substances that are sources of aldehyde compounds such as hexamethylenetetramine, etc. can be used.
Aldehydes can be used alone or in combination of two or more.

Examples of acidic catalysts include organic acids such as acetic acid and oxalic acid; mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; diethyl sulfuric acid; Sulfonic acid; organic phosphonic acids such as 1-hydroxyethylidene-1,1'-diphosphonic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid can be used.
Acidic catalysts can be used alone or in combination of two or more.

Examples of transition metal catalysts include salts of cobalt, nickel, chromium, manganese, zinc, copper, calcium, magnesium, barium, and the like. Examples of the salt include organic salts such as acetate, halides, and oxides. Specific examples of the salt include zinc chloride, zinc acetate, manganese acetate, magnesium acetate, and magnesium oxide.
The transition metal catalysts can be used alone or in combination of two or more.

The resol type phenolic resin is not particularly limited. For example, it can be obtained by reacting the above-mentioned phenols and aldehydes with an alkaline catalyst (under alkaline conditions) or a zinc-based catalyst (under weakly acidic conditions).

Examples of the modified phenol resin include phenoxy-modified phenol resins, and among them, phenoxy-modified novolac type phenol resins are preferred. This makes it easier to improve strengths such as tensile strength, bending strength, and toughness.
Further, in the phenoxy-modified phenol resin, it is preferable that 5 to 25% by mass of the phenol resin is modified with the phenoxy resin. The phenoxy-modified novolac type phenol resin can be synthesized by, for example, dissolving the novolac type phenol resin and the phenoxy resin in an organic solvent and stirring and mixing them, or using a pressure kneader, roll, single-screw or twin-screw kneader, etc. An example of this is melt-kneading.

Examples of epoxy resins include bisphenol epoxy resins (e.g., bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, water-added bisphenol A epoxy resin, dimer acid-modified bisphenol epoxy resin, etc.), novolac type epoxy resins (e.g., phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, etc.), naphthalene type epoxy resins, fluorene type epoxy resins (e.g., bisarylfluorene type epoxy resins, etc.), triphenylmethane type epoxy resins Aromatic epoxy resins such as epoxy resins (e.g. trishydroxyphenylmethane type epoxy resins), nitrogen-containing epoxy resins such as triepoxypropyl isocyanurate (triglycidyl isocyanurate), hydantoin epoxy resins, e.g. Examples include group-based epoxy resins, alicyclic epoxy resins (for example, dicyclocyclic epoxy resins, etc.), glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and the like. By using such an epoxy resin, for example, the dispersibility of the filler can be improved.

Phenoxy resin refers to a resin obtained by polymerizing a low molecular weight epoxy compound through hydroxypolyether bonds. Phenoxy resin has thermoplastic properties by polymerizing epoxy resin, which is a thermosetting resin, through hydroxypolyether bonds. The phenoxy resin preferably has a functional group at its terminal and/or inside, and is more preferably a bifunctional resin having an epoxy group at both terminals.
Phenoxy resins are, for example, hydroxypolyethers synthesized from bisphenols and epichlorohydrin, hydroxypolyethers synthesized from bisphenols and bifunctional epoxy compounds, or bisphenol-type epoxy compounds and dihydric alcohol compounds. It may also be a hydroxy polyether that is synthesized from more.
The phenoxy resin is not particularly limited, but includes phenoxy resins having a bisphenol skeleton, phenoxy resins having a novolak skeleton, phenoxy resins having a naphthalene skeleton, phenoxy resins having a biphenyl skeleton, and the like. Furthermore, a phenoxy resin having a structure having multiple types of these skeletons can also be used. By combining a phenoxy resin with a polymer that contains structural units derived from cyclic olefins in its molecules, the rigidity resulting from the epoxy compound and the flexibility resulting from the hydroxypolyether bond contribute, making it possible to bond at low temperatures. It is estimated that a molding material with high strength and excellent strength can be obtained.

Among these, phenoxy resins having a bisphenol skeleton can be used.

- Thermoplastic resin There are no particular limitations on the thermoplastic resin that can be used. For example, polystyrene resin, polyolefin resin (polyethylene resin, polypropylene resin, etc.), polyester resin (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), polycarbonate resin, vinyl chloride resin, polyacetal resin, etc. can be mentioned.

- Particularly preferred resin The resin preferably includes a phenol resin. Phenol resin is preferably used from the viewpoint of melting characteristics during molding and quality of the final molded product. Among phenol resins, resol type phenol resins are particularly preferred.

The molding material of this embodiment may contain only one resin, or may contain two or more resins.
The amount (ratio) of the resin in the molding material of this embodiment is, for example, 10 to 99% by mass, preferably 20 to 95% by mass, and more preferably 30 to 90% by mass.

(Compound A)
Compound A is not particularly limited as long as it has a hydrocarbon group having 2 or more carbon atoms and an amino group in one molecule.

Examples of the hydrocarbon group having 2 or more carbon atoms include a straight chain or branched alkyl group, a cycloalkyl group, a monovalent alicyclic group, an aryl group, an aralkyl group, and the like. Further, the hydrocarbon group may be a divalent or higher valent group (specifically a divalent to tetravalent group) obtained by further removing a hydrogen atom from these monovalent groups.
By the way, when a straight chain or branched alkyl group is used as a hydrocarbon group having two or more carbon atoms, the action of the straight chain or branched alkyl group causes Compound A to form on the surface of the molded product when the molding material is melted and molded. may become unevenly distributed. This may further improve the releasability from the mold and the adhesion to the coating film of the molded product.

From the viewpoint of performance balance, the number of carbon atoms in the hydrocarbon group is preferably 2 to 30, more preferably 6 to 26, and still more preferably 10 to 24.
From the viewpoint of performance balance, the number of hydrocarbon groups having 2 or more carbon atoms in one molecule of compound A is preferably 1 to 3, more preferably 1 to 2.
From the viewpoint of performance balance, the total number of carbon atoms in one molecule of compound A is, for example, 2 to 60, preferably 4 to 40.

An amino group is, in a narrow sense, a monovalent group represented by -NH ₂ , and in this embodiment, a group represented by -NH ₂ is also preferred. On the other hand, from the viewpoint of improving the coating adhesion of molded articles, the amino group is not necessarily limited to the monovalent group represented by -NH ₂ . That is, in this embodiment, the amino group can be -NR ₂ (the two R's are each independently a hydrogen atom or a monovalent organic group). Here, examples of the monovalent organic group for R include a linear or branched alkyl group, a cycloalkyl group, a monovalent alicyclic group, an aryl group, an aralkyl group, and the like.

Preferable examples of compound A include ethylenediamine, laurylamine, behenylamine, oleylpropylenediamine, and behenylpropylenediamine.
Compound A is available from NOF Corporation and others. For example, behenylpropylene diamine is sold by NOF Corporation under the trade name "Nissan Amine DV Flake."

The molding material of this embodiment may contain only one compound A, or may contain two or more compounds A.
The amount (ratio) of compound A in the molding material of this embodiment is preferably 1 to 5% by mass, more preferably 1 to 3% by mass, and even more preferably 1 to 2% by mass. By appropriately adjusting the amount of compound A, it is possible to further improve the ease of industrial production of the molding material, the ease of releasing it from the mold during molding, and the coating film adhesion of the resulting molded product. . Furthermore, by not using too much compound A, the mechanical properties of the molded article can be improved.

(hardening aid)
The molding material of this embodiment preferably contains a hardening aid. In particular, the curing aid is preferably used when the molding material contains a thermosetting resin or when the molding material contains a thermoplastic resin and a crosslinking agent.

The curing aid is not particularly limited as long as it can accelerate the curing speed when molding the molding material by heating it. The curing aid may be appropriately selected depending on the type of resin used.
An example of the curing aid is an inorganic basic compound. Specific examples include hydroxides of alkali metals, oxides and hydroxides of alkaline earth metals and magnesium. More specifically, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, and aluminum hydroxide can be mentioned.
Other examples of curing aids include organic phosphine compounds such as triphenylphosphine and tributylphosphine, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as phthalic acid, inorganic basic compounds, and organic basic compounds. Basic compounds and the like can also be mentioned.

When the molding material of this embodiment contains a hardening aid, it may contain only one hardening aid, or it may contain two or more hardening aids.
When the molding material of the present embodiment contains a curing aid, the amount (ratio) thereof is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the entire molding material. By using an appropriate amount of the curing aid, it is possible to sufficiently obtain the effects of using the curing aid while minimizing various performance deteriorations.

(filler)
The molding material of this embodiment preferably contains a filler.
An appropriate filler can be selected depending on the intended use and characteristics of the molded product.
The filler may be an inorganic filler or an organic filler, but an inorganic filler is preferable from the viewpoint of heat resistance and durability.

As an example, the filler can include a fibrous filler. Specific examples thereof include glass fiber, carbon fiber, rock wool, and the like. Among these, it is preferable to use glass fiber. As the fibrous filler, it is preferable to use, for example, one having a number average fiber diameter of 10 to 15 μm and a number average fiber length of 1 to 3 mm; More preferably, the diameter is 3 mm. By doing so, the workability during production of the molding material and the mechanical strength of the obtained molded product can be further improved.

As another example, the filler can include particulate, more specifically spherical filler. Specific examples thereof include glass beads, glass powder, calcium carbonate, silica, aluminum hydroxide, clay, and the like.

When the molding material of the present embodiment contains a filler, the amount (ratio) of the filler is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, based on the entire molding material. By using an appropriate amount of filler, the effects of using the filler can be sufficiently obtained while minimizing various performance deteriorations.

(Release agent)
The molding material of this embodiment preferably contains a mold release agent. As the mold release agent, those known in the field of molding materials can be used without particular limitation.
Specific examples include natural waxes such as carnauba wax, synthetic waxes such as montanic acid ester wax and oxidized polyethylene wax, higher fatty acids such as zinc stearate and their metal salts, paraffin, and the like.

When using a mold release agent, only one type may be used, or two or more types may be used.
When a mold release agent is used, its content is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, based on the entire molding material. Thereby, the effect of improving mold releasability can be sufficiently obtained while sufficiently suppressing deterioration of various performances.

(Other ingredients)
The molding material of this embodiment may contain any components other than the components mentioned above. Examples of optional components include low stress agents, colorants, antioxidants, anticorrosive agents, dyes, pigments, flame retardants, and elastomers.
In the examples described below, carbon black is used as a pigment.
Furthermore, in the examples described below, alkyl acetalized polyvinyl alcohol is used as the elastomer. By using an elastomer, the toughness of the resulting molded product can be improved. Furthermore, the presence of functional groups in the elastomer may further improve the adhesion to the coating film.

(Application)
The molding material of this embodiment is preferably used for manufacturing a molded article having a molded article and a coating film formed on at least a portion of the surface of the molded article.
The type of article is not particularly limited. The articles can be various daily necessities, containers, structural members, electronic parts, vehicle parts, and the like.

(Method for manufacturing molding material)
The molding material of this embodiment can be manufactured, for example, by mixing the above-mentioned components in a kneading device while heating them.
As the kneading device, for example, a two-roll mill, a three-roll mill, etc. can be used. The heating temperature and heating time during kneading may be such as long as the chemical reaction (change in quality) of the components to be kneaded can be suppressed. Specific examples of kneading conditions are described in Examples below.
As a precaution, it is preferable to mix each component sufficiently and uniformly before kneading. Various known mixers can be used for mixing.

A kneaded product kneaded using a two-roll mill or a three-roll mill usually becomes a sheet. By pulverizing this sheet-like kneaded material to a desired particle size, a powder or granular molding material can be obtained. Incidentally, the pulverized molding material may be processed into a shape such as a tablet shape.

<Method for manufacturing articles>
Formed on at least part of the surface by a molding process of manufacturing a molded product using the above-mentioned molding material and a coating film forming process of forming a coating film on at least part of the surface of the molded product. An article (molded article) having a coated film can be manufactured.

The molding process is usually performed by heating and melting the above-mentioned molding material. Specifically, a molded article can be manufactured by applying a known molding method such as transfer molding or compression molding.

By applying a coating to the surface of the obtained molded product, an article (molded product) having a coating film can be manufactured.
The type of material (paint) for forming the coating film is not particularly limited. Any paint can be used as long as it can form a coating film on the surface of the molded article.
In terms of the main component of the paint, examples include epoxy resin paint, urethane resin paint, fluororesin paint, polyester resin paint, silicone resin paint, acrylic resin paint, etc., but usable paints are not limited to these.
The paint may be an organic solvent-based paint or a water-based paint (a paint whose main volatile component is water).

The method of forming the coating film is also not particularly limited. Any application method can be selected, including application with a brush, spray application, curtain application, spin application, and application using a bar coater.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and the present invention includes modifications, improvements, etc. within a range that can achieve the purpose of the present invention.

Embodiments of the present invention will be described in detail based on Examples and Comparative Examples. It should be noted that the present invention is not limited only to the embodiments.

<Raw materials>
The following raw materials were prepared.
・Resin resol type phenolic resin: “PR-53529” manufactured by Sumitomo Bakelite Co., Ltd.
・Hardening aid Calcium hydroxide: “Slaked lime SA074” manufactured by Chichibu Lime Industries Co., Ltd.
・Inorganic base material (filler)
Glass fiber: “CS3E479” manufactured by Nittobo Co., Ltd.
・Organic base material Alkyl acetalized polyvinyl alcohol: “S-LEC BL-1” manufactured by Sekisui Chemical Co., Ltd.
・Mold release agent Carnauba wax: Kato Yoko Co., Ltd. “Carnauba Special No. 2 Powder”
・Pigment Carbon: “Carbon Black #750B” manufactured by Mitsubishi Chemical Corporation

・As Compound A, the following was prepared.
Ethylenediamine H ₂ N-C ₂ H ₄ -NH ₂
Laurylamine C ₁₅ H ₂₅ -NH ₂
Behenylamine C ₂₂ H ₄₅ -NH ₂
Oleyl propylene diamine C ₁₈ H ₃₅ -NH-C ₃ H ₆ -NH ₂
Behenylpropylene diamine C ₂₂ H ₄₅ -NH-C ₃ H ₆ -NH ₂

<Production of molding material and evaluation of ease of industrial production of molding material (adhesion to kneading rolls)>
First, a mixture containing the components listed in the "Formulation" column of Table 1 was prepared.
Then, each mixture was kneaded using heated rolls (two-roll mill) having different rotational speeds, formed into a sheet, and cooled.
Thereafter, the cooled sheet-like mixture was ground. This produced a granular molding material (solid at 25°C).

In the above step, the kneading conditions of the heating rolls (two-roll mill) were such that the rotation speed was 20/14 rpm on the high speed side/low speed side, and the temperature was 80/20°C on the high speed side/low speed side. The kneading time was adjusted between 5 and 20 minutes in order to adjust the fluidity to a predetermined level.

When the molding material was manufactured under the above conditions, the time from the start of kneading until the deposits on the heating roll could no longer be visually confirmed was evaluated. It can be said that the shorter this time, the less likely the raw materials will adhere to the kneading device, that is, the better the industrial productivity will be.
Note that the actual kneading was continued for an additional 1 to 7 minutes after the deposits on the heating roll could no longer be visually confirmed in order to adjust the fluidity as described above.

<Evaluation of moldability (ease of injection molding)>
Using the molding material produced above, moldability was evaluated in the following manner.

First, using a 100-ton injection molding machine (manufactured by Toshiba Machine Co., Ltd., screw diameter φ40 mm), a test piece with a capacity of 90 cc was continuously molded for 10 shots (conditions: cylinder temperature 90°C, mold temperature 175°C, injection time 6 seconds). , curing time 50 seconds).
Thereafter, the molten resin material was left in an injection molding machine in a weighed state, and injection was performed after a predetermined period of time had elapsed. When molding was carried out by changing the standing time in 60 second increments, the longest standing time until the molten material could flow and sufficiently fill the mold was determined.
Those that could be sufficiently filled after being left for 5 minutes or more were rated as ○ (good), and those that could not be filled were rated as × (bad).

<Evaluation of paint film adhesion>
The coating film adhesion was evaluated by the following two evaluation methods.
(Paint peeling test)
First, using the molding material produced above, a molded product of Φ100×2 mm was obtained by performing an annealing treatment after molding with a transfer molding machine. A water-based polyurethane paint was spray applied to the surface of this molded article and baked to form a coating film.
At this time, the temperature of the annealing treatment was 180° C. and the treatment temperature was 8 hours. As the water-soluble polyurethane paint, "Hydran HW-350" manufactured by DIC was used. The drying temperature after spray coating was 150° C., and the baking time was 1 hour.

A tape was attached to the coated film after firing, and when the coated film was pulled with a certain force, the tape was rated as ○ (good) if the film did not peel off from the molded product, and the tape was rated as × (bad) if it peeled off.

(Wettability: wet length)
First, using the molding material produced above, a molded product with dimensions of 80 x 10 x 4 mm was obtained by performing an annealing treatment after molding with a transfer molding machine. 140 μL of a water-soluble polyurethane paint diluted to 1% with pure water was dropped onto the edge of this molded article. Then, when the dropped paint was stretched with a cotton swab from one end of the molded product to the other end, the maximum length of the droplet being connected in a straight line without being repelled was measured.
At this time, the temperature of the annealing treatment was 180° C. and the treatment temperature was 8 hours. As the water-soluble polyurethane paint, "Hydran HW-350" manufactured by DIC was used.
It can be said that the longer the maximum length measured here, the greater the affinity between the surface of the molded article and the paint, and the better the adhesion of the paint film.

<Evaluation of mechanical properties of molded products>
The mechanical properties of the molded products were also evaluated. Specifically, the bending strength (MPa) and bending elastic modulus (GPa) of a test piece prepared according to JIS K 6911 were measured in a 150°C atmosphere.

Table 1 summarizes the formulation of the molding materials and the evaluation results.
In "Formulation" in Table 1, the unit of amount of each component is mass %.

Table 1 shows that molding materials that contain resin and compound A and are solid at 25°C do not easily adhere to the kneading rolls during production, and have good injection moldability when producing molded products by injection molding. Moreover, the coating film adhesion of the obtained molded article was good. In other words, a molding material that contains resin and compound A and is solid at 25°C is easy to manufacture industrially, has good molding properties, and has good coating film adhesion in the resulting molded product. It has been shown.

On the other hand, when compound A was not used as in Comparative Example 1, the results of evaluation of adhesion to the kneading roll were poor.
Moreover, in Comparative Example 2, since a large amount of mold release agent was used, the results of the evaluation of adhesion to the kneading roll and the evaluation of moldability were good, but the evaluation results of coating film adhesion were poor.

From the above, by using Compound A, it is possible to "improve the adhesion of the coating film of molded products", "ease of industrial production of molding materials for manufacturing molded products", and "industrial production of molding materials for manufacturing molded products". It is understood that it is possible to strike a balance between performance and ease of molding.

A more detailed analysis of the examples reveals that Examples 1 to 5, in which the usage ratio of compound A is 1.2% by mass, are better than Example 6, in which the usage ratio of compound A is 2.4% by mass. The evaluation results of mechanical properties are shown. From this, it is understood that by appropriately adjusting the usage ratio of Compound A, in addition to achieving the above-mentioned performance balance, it is possible to further improve the mechanical strength of the molded product.

Claims (10)

resin and
A compound A having a hydrocarbon group having 2 or more carbon atoms and an amino group in one molecule,
A molding material that is solid at 25°C. The molding material according to claim 1,
A molding material in which the number of carbon atoms in the hydrocarbon group is 30 or less. The molding material according to claim 1 or 2,
A molding material in which the compound A contains at least one selected from the group consisting of ethylenediamine, laurylamine, behenylamine, oleylpropylenediamine, and behenylpropylenediamine. The molding material according to claim 1 or 2,
A molding material in which the content of the compound A is 1 to 5% by mass. The molding material according to claim 1 or 2,
A molding material in which the resin includes a phenolic resin. The molding material according to claim 1 or 2,
Furthermore, molding materials containing curing aids. The molding material according to claim 1 or 2,
Molding materials that also contain fillers. The molding material according to claim 1 or 2,
A molding material that also contains a mold release agent. The molding material according to claim 1 or 2,
A molding material used for manufacturing a molded article, which includes a molded article and a coating film formed on at least a portion of the surface of the molded article. A molding step of manufacturing a molded article using the molding material according to claim 1 or 2,
a coating film forming step of forming a coating film on at least a portion of the surface of the molded article using a paint;
A method of manufacturing an article, including: